TW201127895A

TW201127895A - Electrically conductive polymer compositions

Info

Publication number: TW201127895A
Application number: TW099120526A
Authority: TW
Inventors: Che-Hsiung Hsu; Ralph Birchard Lloyd; Adam Fennimore; Michael Henry Howard Jr
Original assignee: Du Pont
Priority date: 2009-12-21
Filing date: 2010-06-23
Publication date: 2011-08-16
Also published as: WO2011087818A3; KR20120108007A; US20110147719A1; EP2517210A4; WO2011087818A2; JP2013515157A; CN102667960B; EP2517210A2; CN102667960A; US8282861B2; JP5788901B2

Abstract

The present invention relates to electrically conductive compositions, and their use in electronic devices. The composition includes either (1) a deuterated electrically conductive polymer doped with a highly-fluorinated acid polymer; or (2) (a) a deuterated electrically conductive polymer doped with a non-fluorinated polymeric acid and (b) at least one highly-fluorinated acid polymer.

Description

201127895 六、發明說明：【發明所屬之技術領域】本發明-般係關於包含導電聚合物之組成物及其在電子裝置中之用途。【先前技術】電子裝置定義為一包括一活性層之產品類型。有機電子 &置具有至少一有機活性層。此類裝置將電能轉換為輻射如發光二極體、透過電子程序偵測信號、將輻射轉換為電月b如光伏打電池或者包括一或多之有機半導體層。有機發光二極體（0LED)係一有機電子裝置，其包括能夠電致發光的有機層。包含導電聚合物的有機發光二極體 (OLED)可具有下列組態：陽極/緩衝層/電致發光材料/陰極並且在該些電極間具有額外之層。該陽極通常為具有注入電洞至該EL材料之能力的任何材料，像是如銦/錫氧化物（ITO)。可將該陽極選擇性地支撐在—玻璃或塑膠基板 • 上。EL材料包括螢光化合物、螢光與磷光金屬錯合物、共軛聚合物與上述物質之混合物。該陰極通常為具有注入電子至該EL材料之能力的任何材料（像是wCa$Ba)。具有低導電度範圍在1〇:3至ΙΟ-7 S/cm的導電聚合物一般用作為該緩衝層，並直接接觸一導電陰極如ΙΤ〇。對用於電子裝置之改良材料仍轉續有需求。【發明内容】本發明提供一包含以下（1)或（2)其中之一的組成物： 145486.doc 201127895 高度氟化之酸聚 (i)一氘化之導電聚合物，該聚合物摻雜一合物；或者一非氟化之聚 (2)(a)—氘化之導電聚合物，該聚合物摻雜合性酸；以及 (b)至少一高度氟化之酸聚合物。之—的液體組成本發明亦提供一包含以下（1)或（2)其中物： ⑴⑷至少一氘化之導電聚合物，該聚合物摻雜至少一高度氟化之酸聚合物；以及 (b)—氘化之液體介質；或者 (2)(a)至少一氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸； (b) 至少一高度氟化之酸聚合物；以及 (c) 一氘化之液體介質。本發明亦提供-電子裝置，其具有至少一包含該上述組成物之活性層。【實施方式】本文中描述許多態樣與實施例且僅為例示性而非限制性。在閱讀本說明書後，熟習該技術者將瞭解在不偏離本發明之範疇下，亦可能有其他態樣與實施例。根據下述之詳細說明與申請專利範圍，易使該等實施例中之一或多個實施例的其他特徵及益處更加彰顯。詳細說明首先提出術語的定義與闡明，接著說明該氛化之導電聚合物、該高度氟化之酸聚合物、該導電組成物、電子裝 145486.doc 201127895 置，最後提出實例。 1.術語的定義和闡明在提出下述實施例之細節前，先對某些術語加以定義或闡明。一術語「酸聚合物」指一具有酸性基團的聚合物。術語「酸性基團」指一能夠離子化以提供一氫離子予— 布氏驗的基團。術語「導體」及其Μ意指—具有一電性質之層材料、構件或結構，所以電流流過此層材料、構件或結構時不會有顯著的電位下降。此術語意欲包括半導體。在某些實施例中，一導體會形成一導電度至少為1〇.7s/cm之層。術語「氘化」係意指至少一氫經氘所置換。該氘存在為自然豐度之至少100倍。化合物\的一「氘化類似物」與化合物X具有相同的結構’但是具有至少一置換Η的D。_ Υ%經氘化的材料具有γ%的氫經氘所置換。術語「經摻雜」當指稱一導電聚合物時，其意指該導電聚合物具有一聚合性相對離子，以平衡該導電聚合物上的電荷。術語「經摻雜之導電聚合物」係意指該導電聚合物及與該導電聚合物有關的該聚合性相對離子。術語「導電」當指稱一材料時，係意指一内在或本質上能夠導電的材料，而不需要額外添加碳黑或導電金屬粒子。術語「電活性」當指稱一層或材料時，係意指一呈現電 I45486.doc 201127895 子或電輻射性質的層戋 ^ 次材科。在一電子裝置中，一雷爷性材料電性上有助 / 但不限於傳導、二二作。電活性材料之實例包括荷可+ w 斷電荷之材料（其中該電呈：電：：或電洞)，或者在接收輕射時會發出輕射或王現電子-電洞對之濃度包括作又文化的材枓。非活性材料之實例 ⑮化材料、絕緣材料及環境障壁材料。意产此居：材料、構件或結構時，思私此一層、材科、構件或 t， & 偁促進或有利於負電荷遷移通過此一層、材料、構件或結構，而至另一層、材料構件或結構。力層材科、構術語「完全氟化」及「全全氟化」可互換使用，並一化合物中與碳鍵結的所且係才曰丨另^用虱皆經氟所置換。術Si"「ifj度氟化」指一化人 K D物中’至少9〇〇/盥氫可經氟所置換。 ^厌鍵…的術S吾「電洞注入層I岑「觉、门、+ 」次電洞注入材料」係意指在可在 -有機電子裝置中具有—種或以上之功能的導電或= 層或材枓’該4功能包括但不限於平坦化底下之傳輸與/或電荷注入性質、.、主W4何貝，月除雜質如氧或金屬離子，以及其它有利於或改善有機電子裝置之性能㈣樣。術語「電洞傳輸」當指稱一 ^ ( 增材枓、構件或結構時，思才曰此詹、材料、構件式么士 4塞. 構有利於正電荷遷移通過該層、材料、構件或結構之厚度荷損.失。 4㈣效率及低電術語「層」可與術語膜」交換使用’其指—覆蓋一所 145486.doc 201127895 欲區域之塗層。枯裝置-樣大或二二不二寸:制。該區域可與-整個棬，丨、，十土能區域（例如，實際視覺顯示l 及上㈣與—單次像素一樣小。除有另行指示，上述展上述膜可由任何m積技卿成，包、相沉積（連續式及不連續式技術）及熱轉移。、儿積、夜材機電子裝置」係意指一包括—或多之有機層成 #聚α物」思指-具有至少-重複單體單元的材枓。該術語包括僅具有一種類型或物種材201127895 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention generally relates to a composition comprising a conductive polymer and its use in an electronic device. [Prior Art] An electronic device is defined as a product type including an active layer. The organic electron & has at least one organic active layer. Such devices convert electrical energy into radiation, such as light-emitting diodes, detect signals through electronic processes, convert radiation into electricity, such as photovoltaic cells, or include one or more organic semiconductor layers. An organic light emitting diode (OLED) is an organic electronic device comprising an organic layer capable of electroluminescence. An organic light emitting diode (OLED) comprising a conductive polymer can have the following configurations: anode/buffer layer/electroluminescent material/cathode and with additional layers between the electrodes. The anode is typically any material having the ability to inject a hole into the EL material, such as, for example, indium/tin oxide (ITO). The anode can be selectively supported on a glass or plastic substrate. The EL material includes a fluorescent compound, a fluorescent and phosphorescent metal complex, a mixture of a conjugated polymer and the above. The cathode is typically any material (e.g., wCa$Ba) having the ability to inject electrons into the EL material. A conductive polymer having a low conductivity ranging from 1 〇:3 to ΙΟ-7 S/cm is generally used as the buffer layer and is in direct contact with a conductive cathode such as ruthenium. There is still a need for improved materials for electronic devices. SUMMARY OF THE INVENTION The present invention provides a composition comprising one of the following (1) or (2): 145486.doc 201127895 Highly fluorinated acid poly(i) monomized conductive polymer, the polymer is doped Or a non-fluorinated poly(2)(a)-deuterated conductive polymer which is doped with a conjugated acid; and (b) at least one highly fluorinated acid polymer. Liquid composition of the present invention also provides a conductive polymer comprising: (1) or (2): (1) (4) at least one deuterated conductive polymer doped with at least one highly fluorinated acid polymer; and (b) a liquid medium that is deuterated; or (2) (a) at least one electrically conductive polymer doped with a non-fluorinated polymeric acid; (b) at least one highly fluorinated acid polymer And (c) a liquid medium. The invention also provides an electronic device having at least one active layer comprising the above composition. [Embodiment] Many aspects and embodiments are described herein and are merely illustrative and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments may be possible without departing from the scope of the invention. Other features and advantages of one or more of the embodiments will be apparent from the description and appended claims. The detailed description first sets forth the definition and clarification of the term, and then describes the condensed conductive polymer, the highly fluorinated acid polymer, the conductive composition, and the electronic device. Finally, an example is given. 1. Definitions and Clarification of Terms Certain terms are defined or clarified before the details of the following embodiments are presented. The term "acid polymer" refers to a polymer having an acidic group. The term "acidic group" refers to a group capable of ionization to provide a hydrogen ion--Bush test. The term "conductor" and its mean means a layer of material, member or structure having an electrical property such that there is no significant potential drop in current flow through the layer of material, member or structure. This term is intended to include semiconductors. In some embodiments, a conductor forms a layer having a conductivity of at least 1 7.7 s/cm. The term "deuterated" means that at least one hydrogen is replaced by a hydrazine. The mites are present at least 100 times the natural abundance. A "deuterated analog" of the compound \ has the same structure as the compound X but has at least one D which is substituted for hydrazine. _ Υ% of the deuterated material has γ% hydrogen replaced by hydrazine. The term "doped" when referring to a conductive polymer means that the conductive polymer has a polymeric relative ion to balance the charge on the conductive polymer. The term "doped conductive polymer" means the conductive polymer and the polymerizable counterion associated with the conductive polymer. The term "conducting" when referring to a material means a material that is inherently or essentially electrically conductive, without the need for additional carbon black or conductive metal particles. The term "electrically active" when referring to a layer or material means a layer that exhibits electrical properties or electrical radiation properties. In an electronic device, a material of a thunder is electrically helpful, but not limited to, conduction, two or two. Examples of electroactive materials include materials that can be charged with a charge (wherein the electricity is: electricity:: or a hole), or when a light shot is received, a light shot or a king electron-hole pair concentration is included. And the material of culture. Examples of inactive materials 15 materials, insulating materials and environmental barrier materials. In the case of materials, components or structures, this layer, material, component or t, &; promotes or facilitates the transfer of negative charges through this layer, material, component or structure, to another layer, material Component or structure. The term "completely fluorinated" and "fully fluorinated" are used interchangeably, and the carbon-bonded ones in a compound are replaced by fluorine. Si" "ifj degree fluorination" means that at least 9 〇〇/盥 of hydrogen in a human KD can be replaced by fluorine. ^ 厌 ... 的吾「电电电电电电电电电电电电电电电电电电电电电电电电觉觉觉觉觉觉觉觉觉觉觉觉觉觉觉觉电电电电电Layer or material 'This 4 functions include, but are not limited to, transmission and/or charge injection properties under planarization, . . . , main impurities, such as oxygen or metal ions, and other beneficial or improved organic electronic devices. Performance (four). The term "hole transmission" refers to a material (component, structure, or structure) that is considered to be a material, a material, or a member of the structure. The structure facilitates the migration of positive charges through the layer, material, member, or structure. Thickness loss. Loss. 4 (4) Efficiency and low electricity The term "layer" can be used interchangeably with the term "film" to cover a coating of a region of 145486.doc 201127895. The device is too large or two or two. Inch: system. This area can be as small as - the entire 棬, 丨, and ten earth energy areas (for example, the actual visual display l and the upper (four) and - single pixel. Unless otherwise indicated, the above film can be any m product. Technician, package, phase deposition (continuous and discontinuous technology) and heat transfer., child product, night machine electronic device" means that one or more organic layers into #聚α物- a material having at least - repeating monomer units. The term includes only one type or species

聚合物，或者呈古不你4、平兀的同7L …、#兩種或以上之不同單體單元的共聚合物，包括由不同物種之單體單元所形成之共聚合物。雖然發光材料亦可具有某些電荷輸送性質，但術語「電洞傳輸J與「電子傳輸J不意欲包括主要功能為發光之層、材料、構件或結構。如本文中所用者，術語「包含」、「包括」、「具有」或其任何其他變型意欲涵蓋一非排他性的包括。例如，含有一 -牛月單# t耘、方法、製品或裝置不必然僅限於清單 ^所列出的這些元件而已’而是可以包括未明確列出但卻疋D亥製耘、方法、製品或裝置所固有的其他元件。此外，除非另有明確相反陳述’否則「或J指一包含性的或」，而不是指一排他性的「或」。例如，一八或B之情況係為下述任一所滿足·· A是真（或存在的）且B是偽（或不存在的）A疋傷（或不存在的）且B是真（或存在的），以及A 和B都是真（或存在的）。 145486.doc 201127895 又，使用「一 (a or an)來描述本文中所述的元件和組件。14樣做僅僅是為了方便，並且對本發明範疇提供一般性的意義。除非报明顯地另指他意，這種描述應被理解為包括一或至少一’並且該單數也同時包括複數。對應於7C素週期表中之攔的族編號使用如 Handbook of Chemistry and Physics, 81st Edition (2000-2〇01)中所載之「新符號（New Notation)」規範。除非另有定義，本文所用之所有技術與科學術語均與本發明所屬技術領域具有一般知識者所通常理解的意義相同。在式中，字母(^、11、丁、貿、又、丫與2用以代表文中所定義的原子或基團。所有其它的字母代表現有的原子符號°對應於元素週期表中之攔的族編號使用如於办ooA: 〇/ CAem⑸抑少们以，81st Edition (2000)中所載之「新符號（New Notation)」規範。在本文未描述之範圍内，許多關於特定材料、加工行為 (processing act)及電路的細節係習知的，且可在有機發光二極體顯示器、光源、光偵測器、光伏打及半導性構件技術領域的教科書及其他資料中找到。 2.氘化之導電聚合物該氘化之導電聚合物具有至少一 D。所謂「氘化之導電聚合物」’其意謂該導電聚合物本身（不包括相關的聚合性酸）係氣化。在某些實施例中，該導電聚合物係至少1 〇%經氘化。此意謂至少10%的Η經D所置換。在某些實施例中，該化合物係至少20%經氘化；在某些實施例中，至少3〇% 145486.doc 201127895 氘化，在某些實施例中，至少4〇%經氘化；在某些實施例中，至少50%經氘化；在某些實施例中，至少6〇%經氘化’在某些實施例中，至少鳩經氘化；在某些實施例中’至少8〇%經氛化；在某些實施例中，至少9㈣經氣化。在某些實施例中，該導電聚合物為100。/。經氘化。任何氘化之導電聚合物可用於此新的組成物。在某些實 ' 力例中，該氣化之導電聚合物會形成一膜，該膜之導電度 - 為大於l〇.7S/cm。又 e亥適用於此新組成物之氖化導電聚合物係由i少一種單體所製成’該單體在單獨聚合時會形成一導電同元聚合物。本文中稱此類單體為「導電先質單體」。在單獨聚: ::形成一不導電同元聚合物的單體，係稱為「非導電先貝單體s亥氘化之導電聚合物可為一同元聚合物或一共聚口物。該適用於此新組成物之乱化導電共聚合物可由兩種或以上之導電先質單體所製成，或者由一種或以上之導電先質單體與一種或以上之非導電先質單體的組合所製 * 成。 •、該讥化之導電聚合物可由氘化之導電先質單體所製成。或者，職化之導電聚合物可由非氣化導電先質單體所製成’接著在聚合後經氘化。在某些實施例中，該氘化之導電聚合物係由至少—先質早體所製成，該先質單體係選自噻吩、硒吩、碲吩、吡咯、苯胺、4_胺基·十朵、7_胺基令朵、多環芳族以及上述物質之氛化類似物。由這些單體所製成的聚合物在本文 145486.doc 201127895A polymer, or a copolymer of different monomer units of the same 7L, or two or more, including a copolymer formed of monomer units of different species. Although the luminescent material may also have certain charge transport properties, the terms "hole transport J and "electron transport J are not intended to include layers, materials, members or structures whose primary function is to illuminate. As used herein, the term "includes". , "including", "having" or any other variation thereof is intended to cover a non-exclusive inclusion. For example, the inclusion of a - 牛月单#t耘, method, article, or device is not necessarily limited to the elements listed in the list, but may include, but not explicitly listed, methods, articles Or other components inherent in the device. In addition, unless otherwise stated to the contrary, otherwise "or J refers to an inclusive or" rather than an exclusive "or". For example, the case of one or eight or B is satisfied by any of the following: A is true (or existing) and B is a pseudo (or non-existent) A flaw (or non-existent) and B is true ( Or existing), and A and B are both true (or existing). 145486.doc 201127895 Again, the use of "a or an" to describe the elements and components described herein is for convenience only and provides a general sense of the scope of the invention unless expressly stated otherwise. This description should be understood to include one or at least one ' and the singular also includes the plural. The family number corresponding to the block in the 7C prime table is used, for example, Handbook of Chemistry and Physics, 81st Edition (2000-2〇01) The "New Notation" specification contained in ). Unless defined otherwise, all technical and scientific terms used herein have the same meaning meaning In the formula, the letters (^, 11, D, TT, 丫, 丫 and 2 are used to represent the atoms or groups defined in the text. All other letters represent the existing atomic symbols ° correspond to the blocks in the periodic table. The family number is used as the ooA: 〇 / CAem (5) and the "New Notation" specification contained in the 81st Edition (2000). In the scope not described in this article, many about specific materials, processing behavior The details of the processing act and the circuit are well known and can be found in textbooks and other materials in the field of organic light-emitting diode displays, light sources, photodetectors, photovoltaic and semi-conductive components. Conductive polymer The conductive polymer having at least one D. The so-called "deuterated conductive polymer" means that the conductive polymer itself (excluding the associated polymeric acid) is vaporized. In some embodiments, the conductive polymer is deuterated by at least 1%. This means that at least 10% of the ruthenium is replaced by D. In certain embodiments, the compound is at least 20% deuterated; In some embodiments, at least 3〇% 145486.doc 201127895 Deuteration, in some embodiments, at least 4% is deuterated; in some embodiments, at least 50% is deuterated; in some embodiments, at least 6% is deuterated 'in a certain In some embodiments, at least 鸠 is deuterated; in some embodiments 'at least 8% by centrifugation; in some embodiments, at least 9 (d) is vaporized. In certain embodiments, the conductive polymer It is 100%. Any deuterated conductive polymer can be used for this new composition. In some real cases, the vaporized conductive polymer forms a film, and the conductivity of the film - is greater than l〇.7S/cm. The e-coupling conductive polymer suitable for this new composition is made of less than one monomer. 'The monomer will form a conductive homopolymer when polymerized separately. In this paper, such a monomer is referred to as a "conductive precursor monomer." In a single polymerization: :: a monomer that forms a non-conductive homopolymer is called a "non-conductive scallop monomer." The conductive polymer may be a homopolymer or a copolymer. The disordered conductive copolymer suitable for the new composition may be two or more. Made of a conductive precursor, or a combination of one or more conductive precursors and one or more non-conductive precursors. • The vaporized conductive polymer can be deuterated Alternatively, the electrically conductive polymer may be made of a non-vaporized electrically conductive precursor monomer' followed by deuteration after polymerization. In certain embodiments, the deuterated The conductive polymer is made of at least a precursor, the precursor system is selected from the group consisting of thiophene, selenophene, porphin, pyrrole, aniline, 4-amino group, ten, 7-amino ketone, Polycyclic aromatics and singular analogs of the above substances. Polymers made from these monomers are herein 145486.doc 201127895

的單體包含下式I :The monomer contains the following formula I:

其中： Q係選自由S、Se與Te所組成之群組； R係經獨立選擇因此在每次出現時為相同或不同，並且係選自氫、氘、烷基、烯基、烷氧基、烷醯基、烷硫基、芳氡基、烷硫烷基、烷芳基、芳烷基、胺基、烷胺基、二烷胺基、芳基、烷亞磺醯基、烷氧烧基、烧磺醯基、芳硫基、芳亞磺醯基、烷氧幾基、芳續醯基、丙稀酸、鱗酸、膦酸、鹵素、硝基、氰基、經基、環氧基、石夕烧、石夕氧烧、醇、节基、叛酸鹽、喊、醚叛酸鹽、gt胺續酸鹽、醚續酸鹽、酯磺酸鹽與胺曱酸乙酯；或者兩個R1基團可— 起形成一伸炫•基或伸烯基鏈，其完成一3、4、5、6 145486.doc • 10- 201127895 或7貝芳環或月旨環，該環可選擇性地包括-或多個之Wherein: Q is selected from the group consisting of S, Se and Te; R is independently selected so that it is the same or different at each occurrence, and is selected from the group consisting of hydrogen, hydrazine, alkyl, alkenyl, alkoxy , alkanoyl, alkylthio, arylalkyl, alkylsulfanyl, alkaryl, aralkyl, amine, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxy Base, sulfonyl, arylthio, arylsulfinyl, alkoxy, aromatic, acrylic acid, phthalic acid, phosphonic acid, halogen, nitro, cyano, thiol, epoxy Base, Shi Xizhuo, Shixi Oxygen, alcohol, benzyl, tartrate, shout, ether tartrate, gt amine, ether hydrochloride, ester sulfonate and ethyl citrate; or The two R1 groups may form a stretchable or extended alkenyl chain which completes a 3, 4, 5, 6 145486.doc • 10- 201127895 or 7-shell ring or a moon ring, which may be selected Sexually includes - or more

Hi'碲'硫或氧原子；以及 R2為Η或D。巾所用者’術語「烷基」係指-衍生自脂族烴的 …且包括未經取代或經取代的直鏈、支鏈及環狀基團術居「雜垸基」係意指一烧基基團，其中在該燒基基團内的-或多個之碳原子已經另一原子置換，％氮、氧、爪及類似者。術語「伸烷基」指一具有兩個鍵結點的烷基基團。士本文中所用者，術語「稀基」指一衍生自具有至少一碳-碳雙鍵之脂族烴的基團，且包括未經取代或經取代的直鏈、支鏈及環狀基團。術語「雜烯基」係意指一烯基基團，其中在該烯基基團内的一或多個碳原子已經另—原子置換，如氮、氧、硫及類似者。術語「伸烯基」指—具有兩個鍵結點的烯基基團。如本文中所用者，下列用於取代基基團之術語係指以下所給出之式：「醇」「醯胺基」「醯胺磺酸鹽」「苄基」羧酸鹽」「醚」「醚羧酸鹽」 r'醚磺酸鹽」「酯磺酸鹽」「磺醯亞胺」「胺曱酸乙酯」 -r3-oh -R3-C(0)N(R6)R6Hi'碲' sulfur or oxygen atom; and R2 is Η or D. The term "alkyl" as used in the term "alkyl" means - derived from an aliphatic hydrocarbon and includes unsubstituted or substituted linear, branched and cyclic groups. a group in which one or more carbon atoms in the alkyl group have been replaced by another atom, % nitrogen, oxygen, claws and the like. The term "alkylene" refers to an alkyl group having two bond points. As used herein, the term "dilute group" refers to a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond and includes unsubstituted or substituted linear, branched and cyclic groups. . The term "heteroalkenyl" means a monoalkenyl group in which one or more carbon atoms in the alkenyl group have been replaced by another atom, such as nitrogen, oxygen, sulfur and the like. The term "alkenyl" refers to an alkenyl group having two bond points. As used herein, the following terms for a substituent group refer to the formula given below: "Alcohol" "Amidino" "Amidoxime" "Benzyl" Carboxylate "Ether" "Ether carboxylate" r'ether sulfonate "ester sulfonate" "sulfonimide" "ethylamine citrate" -r3-oh -R3-C(0)N(R6)R6

-R3-C(0)N(R6)R4-S03Z -ch2-c6h5 -r3-c(o)o-z 或-r3-o-c(o)-z -R3-(0-R5)p-0-R5 -r3-o-r4-c(o)o-z 或-r3-o-r4-o-c(o)-z -r3-o-r4-so3z -R3-0-C(0)-R4-S03Z -R3-S02-NH- S02-R5 -R3-0-C(0)-N(R6)2 145486.doc 201127895 '、3，冑汉」基團在每次出現時為相同或不同並且： :、、、I鍵或-伸烧基基團R4為—伸烧基基團r5為—貌基基團 R6為氫、氘或一烷基基團 P為〇或一1至20的整數 Z為H、D、鹼金屬、鹼土金屬、N(R5)4或尺5在上述任何 «中，-或多個之Η可經D所置換。上述任何基團可進 ν為未經取代或經取代，並且任何基團可藉由F取代一或夕個之氫，包括全氟化基團。在某些實施例中，該烷基與伸院基基團具有個碳原子。在某些實施例中，該烧基與伸烷基基團係為經氘化。在某些實施例中’於該單體内，兩個Rl 一起形成_w_ (CY1 YbtTVW- ’ 其中 π^2或 3，w為〇、s、Se、P〇、 NR6 ’ Y1在每次出現時為相同或不同並且為氫、沉或氟，以及Y在母次出現時為相同或不同，並且係選自氫、氛、鹵素、烷基、醇、醯胺磺酸鹽、苄基、羧酸鹽、醚、醚羧酸鹽、醚磺酸鹽、酯磺酸鹽與胺甲酸乙酯，其中該些γ基團可部分或全部沉化或部分或全部氟化。在某些實施例中，所有Y皆為氫或氘。在某些實施例中，該導電先質單體為3,4-伸乙二氧噻吩 (3,4-ethylenedioxythiophene，「EDOT」）。在某些實施例中，該導電先質單體為D4-EDOT或D^EDOT，如下所示。 145486.doc 201127895-R3-C(0)N(R6)R4-S03Z -ch2-c6h5 -r3-c(o)oz or -r3-oc(o)-z -R3-(0-R5)p-0-R5 - R3-o-r4-c(o)oz or -r3-o-r4-oc(o)-z -r3-o-r4-so3z -R3-0-C(0)-R4-S03Z -R3-S02 -NH- S02-R5 -R3-0-C(0)-N(R6)2 145486.doc 201127895 ', 3, Aohan' groups are the same or different at each occurrence and: :, ,, I The bond or the pendant group R4 is - the alkyl group r5 is - the radical group R6 is hydrogen, the hydrazine or the monoalkyl group P is 〇 or an integer from 1 to 20, Z is H, D, The alkali metal, alkaline earth metal, N(R5)4 or ruler 5 may be replaced by D in any of the above «, or more than one. Any of the above groups may be unsubstituted or substituted, and any group may be substituted by one or a hydrogen of F, including a perfluorinated group. In certain embodiments, the alkyl group has a carbon atom with the pendant group. In certain embodiments, the alkyl and alkylene groups are deuterated. In certain embodiments, 'in this monomer, two R1 together form _w_(CY1 YbtTVW- ' where π^2 or 3, w is 〇, s, Se, P〇, NR6 'Y1 at each occurrence When the same or different and are hydrogen, sink or fluorine, and Y is the same or different when the mother appears, and is selected from the group consisting of hydrogen, aryl, halogen, alkyl, alcohol, decyl sulfonate, benzyl, carboxy Salts, ethers, ether carboxylates, ether sulfonates, ester sulfonates and urethanes, wherein the gamma groups may be partially or fully precipitated or partially or fully fluorinated. In certain embodiments , all Y are hydrogen or hydrazine. In certain embodiments, the conductive precursor monomer is 3,4-ethylenedioxythiophene ("EDOT"). In certain embodiments The conductive precursor monomer is D4-EDOT or D^EDOT, as shown below. 145486.doc 201127895

D4-ED〇T 由這些材料所製得的 (d6-edot) 〇在某些貫施例中 d6-edot 聚合物分別縮寫為聚（D4-ED〇T)與聚 ’該單體具有式1(a) /C(R7)2)mD4-ED〇T (d6-edot) prepared from these materials. In some embodiments, the d6-edot polymer is abbreviated as poly(D4-ED〇T) and poly'. (a) /C(R7)2)m

(la) R2 其中： Q係4自由s、Se與丁6所組成之群組； R2為Η或D ; R在每次出現時為相同或不同，並且係選自氫、氘、烷基、雜烷基、烯基、雜烯基 '醇、醯胺磺酸鹽、苄基、羧酸鹽、醚、醚羧酸鹽、醚磺酸鹽、酯磺酸鹽與胺甲酸乙酯，但前提是至少一R7非為氫，並且 m 為2或3。在式1(a)的某些貫施例中，^為二，一 r7為—目^ 巧—具有多於5 個碳原子的烷基基團，並且所有其他R7為氫或氘。、工(勾的某些實施例中，至少一R7基團為氟化。式隹某些實施 145486.doc 13 201127895 « 例中至夕—R基團具有至少一敦取代基。在某些實施例中，該R7基團為完全氟化。在式1(a)的某些實施例中，在單體之稠合脂環上的該r7 取代基為該單體提供了改善的水溶性，並且有利於在該氣化酸聚合物存在下進行聚合。在式1(a)的某些實施例中，111為2，一R7為磺酸_伸丙基_ 醚-亞甲基（ulfonic acid-proPylene_ether_methylene)，並且所有其他R7為氫或氘。在某些實施例中，m為2，一 R7為丙基-醚-伸乙基，並且所有其他尺7為氫或氘。在某些實施例中，m為2，一R7為甲氧基，並且所有其他尺7為氫或氘。在某些實施例中，一 R7為磺酸二氟亞甲基酯亞曱基（_CH2_〇_ C(0)-CF2-S03H)，並且所有其他R7為氫或氘。在某些實施例中，預料可用於在該新複合分散液中形成該導電聚合物的°比洛單體包含下列式Η。(la) R2 wherein: Q is a group of 4 free s, Se and butyl 6; R2 is Η or D; R is the same or different at each occurrence, and is selected from the group consisting of hydrogen, hydrazine, alkyl, Heteroalkyl, alkenyl, heteroalkenyl 'alcohol, decyl sulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate and ethyl urethane, but only It is at least one R7 which is not hydrogen and m is 2 or 3. In some embodiments of Formula 1 (a), ^ is two, one r7 is - an alkyl group having more than 5 carbon atoms, and all other R7 is hydrogen or deuterium. In some embodiments, at least one R7 group is fluorinated. Some embodiments 145486.doc 13 201127895 « In the case of the example, the R group has at least one substituent. In some embodiments In one embodiment, the R7 group is fully fluorinated. In certain embodiments of Formula 1 (a), the r7 substituent on the fused alicyclic ring of the monomer provides improved water solubility to the monomer. And it is advantageous to carry out the polymerization in the presence of the gasified acid polymer. In some embodiments of formula 1 (a), 111 is 2, and one R7 is a sulfonic acid _ propyl-ether-methylene (ulfonic acid) -proPylene_ether_methylene), and all other R7 are hydrogen or deuterium. In certain embodiments, m is 2, one R7 is propyl-ether-extended ethyl, and all other nibs 7 are hydrogen or deuterium. In some implementations In the examples, m is 2, one R7 is methoxy, and all other feet 7 are hydrogen or deuterium. In certain embodiments, one R7 is a difluoromethylene sulfonate sulfonate (_CH2_〇_ C(0)-CF2-S03H), and all other R7 are hydrogen or hydrazine. In certain embodiments, it is expected that the conductive polymer can be used to form the conductive polymer in the new composite dispersion. It contains the following formula Η.

在式II中：In Formula II:

Rl係經獨立選擇因此在每次出現時為相同或不同，並且係選自由氫、氘、烷基、烯基、烷氧基、烷醯基、炫碰基、芳氧基、烧硫烧基、燦芳基、芳院基、胺基、烷胺基、二烷胺基、芳基、烷亞磺醯 145486.doc 14 201127895 基、烷氧烷基、烷磺醯基、芳硫基、芳亞磺醯基、貌氧幾基、芳續醯基、丙烯酸、磷酸、膦酸、南素、罐基、氰基、經基、環氧基、砂貌、石夕氧燒、醇、节基、羧酸鹽、醚、醯胺續酸鹽、鍵缓酸鹽、酿磺酸鹽、胺甲酸乙醋與上述物質的氘化類似物所組成之群組；或者兩個R1基團可—起形成一伸烷基或伸稀基鍵’其完成一3、4、5、6或7員芳環或月^ 環，該環可選擇性地包括一或多個之二價氮、硫、砸、碑或氧原子； R2係經獨立選擇因此在每次出現時為相同或不同並且係選自由氫與氘所組成之群組；以及 R係經獨立選擇因此在每次出現時為相同或不同，並且係選自氫、氘、烷基、烯基、芳基、烷醯基、烷硫烷基、烷芳基、芳烷基'胺基、環氧基、矽烷、矽氧院、醇、苄基、羧酸鹽、醚、醚羧酸鹽、醚績酸鹽、酯磺酸鹽、胺曱酸乙酯與上述物質的氘化類似物。在某些實施例中，R1在每次出現時為相同或不同，並且係獨立選自氫、氘、烷基、烯基、烷氧基、環烷基 '環烯基、醇、苄基、羧酸鹽、醚、醯胺磺酸鹽、醚羧酸鹽、醚磺酸鹽、酯磺酸鹽、胺曱酸乙酯、環氧基、矽烷、矽氧烷以及經一或多之下列取代基所取代的烷基，包括磺酸、羧酸、丙烯酸、磷酸、膦酸、鹵素、硝基、氰基、羥基、環氧基、石夕烧或石夕氧烧部分（moieties)。上述任何基團可為經 145486.doc 15 201127895 氘化。在某些貫施例中’ R係選自氮、烧基以及經·一或多之下列取代基所取代的競•基，包括績酸、叛酸、丙烯酸、鱗酸、膦酸、素、氰基、經基、環氧基、梦烧或石夕氧燒部分。在某些實施例中’該°比咯單體為未經取代並且R1、R2與 R8為氫。未經取代之非氘化吼咯在本文中係縮寫為「Py」。在某些實施例中’ R1、R2與R8為氘。該完全氣化之吡咯單體係縮寫為「D^Py」^由此單體所製成之聚合物係縮寫為「聚（D5-Py)」。在式II的某些實施例中’兩個Ri 一起形成一 6或7員脂環’其進一步經一基團所取代，該基團係選自烷基、雜烷基、醇、苄基、羧酸鹽、醚、醚羧酸鹽、醚磺酸鹽、酯確酸鹽、胺甲酸乙酯與上述物質的氘化類似物。這些基團可改善該單體與所得聚合物之溶解性。在某些實施例中，兩個R1—起形成一 6或7員脂環，其進一步經一烷基基團所取代。在某些實施例中’兩個R1 一起形成一 6或7員脂環，其進一步經一具有至少一碳原子的烷基基團所取代。在某些實施例中，兩個Ri —起形成_〇_(CY2)m-〇-，其中 m為2或3，且Y在每次出現時為相同或不同並且選自氫、氘、烷基、醇、苄基、羧酸鹽、醯胺磺酸鹽、醚、醚羧酸鹽、鱗項酸鹽、酯磺酸鹽、胺曱酸乙酯與上述物質的氘化類似物。在某些實施例中，至少一 γ基團為氘。在某些實施例中，至少一 γ基團為一藉由F取代至少一氫的取代基。 145486.doc -16- 201127895 在某些實施例中’至少一 γ基團為全氟化。在某些實施例中，預料可用於在該新複合分散液中形成該導電聚合物的苯胺單體包含下式III。Rl is independently selected so as to be the same or different at each occurrence, and is selected from the group consisting of hydrogen, hydrazine, alkyl, alkenyl, alkoxy, alkoxy, cyclyl, aryloxy, sulphur-burning , aryl, aryl, amine, alkylamine, dialkylamino, aryl, alkylsulfinium 145486.doc 14 201127895 base, alkoxyalkyl, alkanesulfonyl, arylthio, aromatic Sulfosyl, oxy-oxyl, aromatic sulfhydryl, acrylic acid, phosphoric acid, phosphonic acid, nitrite, canister, cyano, thiol, epoxy, sand, oxox, alcohol, benzyl a group consisting of a carboxylate, an ether, a guanidinium salt, a sucrose salt, a sulphonate, an urethane sulphate, and a deuterated analog of the above; or two R1 groups Forming an alkylene group or a dilute base bond' which completes a 3, 4, 5, 6 or 7 membered aromatic ring or a ring, which ring may optionally include one or more of divalent nitrogen, sulfur, hydrazine, a monument or an oxygen atom; R2 is independently selected so that it is the same or different at each occurrence and is selected from the group consisting of hydrogen and helium; and the R system is independently selected so that each occurrence When the same or different, and is selected from the group consisting of hydrogen, hydrazine, alkyl, alkenyl, aryl, alkyl sulfonyl, alkylthioalkyl, alkaryl, aralkyl 'amine, epoxy, decane, hydrazine Oxygen, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether salt, ester sulfonate, ethyl decanoate and deuterated analogs of the above. In certain embodiments, R1 is the same or different at each occurrence and is independently selected from the group consisting of hydrogen, deuterium, alkyl, alkenyl, alkoxy, cycloalkyl 'cycloalkenyl, alcohol, benzyl, a carboxylate, an ether, a decyl sulfonate, an ether carboxylate, an ether sulfonate, an ester sulfonate, an amine decanoate, an epoxy group, a decane, a decane, and one or more of the following substitutions The alkyl group substituted by the group includes a sulfonic acid, a carboxylic acid, an acrylic acid, a phosphoric acid, a phosphonic acid, a halogen, a nitro group, a cyano group, a hydroxyl group, an epoxy group, a sulphuric acid or a moieties. Any of the above groups may be deuterated by 145486.doc 15 201127895. In some embodiments, 'R is selected from the group consisting of nitrogen, alkyl and substituted by one or more of the following substituents, including acid, acid, acid, glycerin, phosphonic acid, A cyano group, a thiol group, an epoxy group, a dream burn or a sulphuric acid. In certain embodiments, the monomer is unsubstituted and R1, R2 and R8 are hydrogen. The unsubstituted non-deuterated hydrazine is abbreviated as "Py" in this article. In certain embodiments 'R1, R2 and R8 are deuterium. The fully vaporized pyrrole single system is abbreviated as "D^Py". The polymer made from this monomer is abbreviated as "poly(D5-Py)". In certain embodiments of Formula II, 'two Ris together form a 6 or 7 membered alicyclic ring' which is further substituted with a group selected from the group consisting of alkyl, heteroalkyl, alcohol, benzyl, Carboxylates, ethers, ether carboxylates, ether sulfonates, ester acid salts, ethyl urethanes and deuterated analogs of the above. These groups improve the solubility of the monomer with the resulting polymer. In certain embodiments, two R1 together form a 6 or 7 membered alicyclic ring which is further substituted with an alkyl group. In certain embodiments, the two R1 together form a 6 or 7 membered alicyclic ring which is further substituted with an alkyl group having at least one carbon atom. In certain embodiments, two Ris together form _〇_(CY2)m-〇-, where m is 2 or 3, and Y is the same or different at each occurrence and is selected from the group consisting of hydrogen, hydrazine, and alkane Base, alcohol, benzyl, carboxylate, decyl sulfonate, ether, ether carboxylate, scale acid salt, ester sulfonate, ethyl amine decanoate and deuterated analogs of the above. In certain embodiments, at least one gamma group is deuterium. In certain embodiments, at least one gamma group is a substituent substituted by at least one hydrogen by F. 145486.doc -16- 201127895 In certain embodiments, at least one gamma group is perfluorinated. In certain embodiments, the aniline monomer that is expected to be useful in forming the conductive polymer in the new composite dispersion comprises Formula III below.

其中： R1係經獨立選擇因此在每次出現時為相同或不同’並且係選自由氫、氘、烷基、烯基、烷氧基、烷醯基、烷硫基、芳氧基、烷硫烷基、烷芳基、芳烷基、胺基、烧胺基、二烧胺基、芳基、烧亞項醯基、烷氧烷基、烷磺醯基、芳硫基、芳亞磺醯基、烧氧幾基、芳續醯基、丙稀酸、鱗酸、膦酸、鹵素、硝基、氰基、羥基、環氧基、矽烷、矽氧烷、醇、苄基、羧酸鹽、醚、醚羧酸鹽、醯胺磺酸鹽、喊磺酸鹽、酯磺酸鹽、胺曱酸乙酯與上述物質的氘化類似物所組成之群組；或者兩個Ri基團可一起形成一伸烷基或伸烯基鏈，其完成一3、4、5、6或7員芳環或脂環，該環可選擇性地包括一或多個之二價氮、硫或氧原子；以及 R2係經獨立選擇因此在每次出現時為相同或不同’並且係選自由氫與氘所組成之群組。在聚合時’該苯胺單體單元具有以下所示之式IV⑷或式IV(b) ’或者兩式之一組合。 145486.doc 201127895 (R1)4Wherein: R1 is independently selected so that it is the same or different at each occurrence and is selected from the group consisting of hydrogen, hydrazine, alkyl, alkenyl, alkoxy, alkoxy, alkylthio, aryloxy, alkanethio Alkyl, alkaryl, aralkyl, amine, acryl, dialkylamine, aryl, pyrenyl, alkoxyalkyl, alkanesulfonyl, arylthio, arylsulfin Base, aerobic acid group, aromatic sulfhydryl group, acrylic acid, scaly acid, phosphonic acid, halogen, nitro group, cyano group, hydroxyl group, epoxy group, decane, decane, alcohol, benzyl, carboxylate a group consisting of an ether, an ether carboxylate, a decyl sulfonate, a sulfonate, an ester sulfonate, an amine phthalate, and a deuterated analog of the above; or two Ri groups Forming an alkyl or extended alkenyl chain together which completes a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring which may optionally include one or more divalent nitrogen, sulfur or oxygen atoms And R2 are independently selected so are the same or different at each occurrence and are selected from the group consisting of hydrogen and hydrazine. The aniline monomer unit at the time of polymerization has the formula IV (4) or the formula IV (b)' shown below or a combination of the two. 145486.doc 201127895 (R1)4

在式III的某些實施例中，該苯胺單體為未經取代且ri與 R2為Η或D。該非氘化之未經取代笨胺單體在本文中係縮寫為「ani」。在某些實施例中，該單體為D5_an^D7_ani，如下所示。In certain embodiments of Formula III, the aniline monomer is unsubstituted and ri and R2 are deuterium or D. The non-deuterated unsubstituted strepamine monomer is herein referred to as "ani". In certain embodiments, the monomer is D5_an^D7_ani, as shown below.

D DD D

NH， D5-ani D ΠNH, D5-ani D Π

ND, 由這些單體製成之聚合物分別縮寫為聚（D5_ani)與聚（D7_ ani) 在式ΙΠ的某些實施例中，至少基團為⑹卜在某些實施例中，至少一 H1為全說化。在某些實施例中’預料可用於在該新複合分散液中形成該氛化之導電聚合物的稠合多環雜芳族單體具有兩個或以 145486.doc 201127895 上之稠〇万環，其中至少一為雜芳族。在某些實施例中该稠合多環雜芳族單體具有式V:ND, polymers made from these monomers are abbreviated as poly(D5_ani) and poly(D7_ani), respectively. In certain embodiments of the formula, at least the group is (6). In some embodiments, at least one H1 For the sake of all. In certain embodiments, a fused polycyclic heteroaromatic monomer that is expected to be useful in forming the condensed conductive polymer in the new composite dispersion has two or a condensed ring of 145486.doc 201127895 At least one of them is heteroaromatic. In certain embodiments the fused polycyclic heteroaromatic monomer has the formula V:

其中： Q 為 S、Se、Te或 NR6 ; R6為氫、氘或烷基； R9' R1()、r11與R>2係經獨立選擇因此在每次出現時為相同或不同，並且係選自氫、烷基、烯基、烷氧基、烧酸基、烷硫基、芳氧基、烷硫烷基、烷芳基、芳烷基、胺基、烷胺基、二烷胺基、芳基、烷亞磺醯基、烷氧烷基、烷磺醯基、芳硫基、芳亞磺醯基、烧氧羰基、芳績醯基、丙烯酸、碌酸、膦酸、_ 素、確基、腈、氰基、經基、環氧基、石夕院、矽氧炫*、醇、苄基、叛酸鹽、趟、趟缓酸鹽、醯胺磺酸鹽、醚磺酸鹽、酯續酸鹽與胺甲酸乙酯；以及 R9與R10、R10與R11以及R11與中之至少一對一起形成一伸烯基鏈，其完成一 5或6員芳環，該環可選擇性地包括一或多個之二價氮、硫、硒、碲或氧原子。在某些實施例中，該稠合多環雜芳族單體具有一式其係選自由 V(a)、V(b)、V(c)、V(d)、V(e)、V(f)、V(g)、 V(h)、V(i)、V(j)與V(k)所組成之群組： 145486.doc -19- 201127895Wherein: Q is S, Se, Te or NR6; R6 is hydrogen, hydrazine or alkyl; R9' R1(), r11 and R>2 are independently selected so they are the same or different at each occurrence, and are selected From hydrogen, alkyl, alkenyl, alkoxy, succinic acid, alkylthio, aryloxy, alkylthioalkyl, alkaryl, aralkyl, amine, alkylamino, dialkylamino, Aryl, alkylsulfinyl, alkoxyalkyl, alkanesulfonyl, arylthio, arylsulfinyl, oxycarbonyl, fluorenyl, acrylic, acid, phosphonic acid, _ Base, nitrile, cyano group, thiol group, epoxy group, Shixiyuan, oxime*, alcohol, benzyl, tartrate, guanidine, sulphonate, decyl sulfonate, ether sulfonate, a transesterate and an urethane; and R9 and R10, R10 and R11, and at least one of R11 and R11 form an extended alkenyl chain which completes a 5 or 6 membered aromatic ring, which ring optionally includes One or more of a divalent nitrogen, sulfur, selenium, tellurium or oxygen atom. In certain embodiments, the fused polycyclic heteroaromatic monomer has a formula selected from the group consisting of V(a), V(b), V(c), V(d), V(e), V( f), group of V(g), V(h), V(i), V(j) and V(k): 145486.doc -19- 201127895

145486.doc -20- 201127895 其中： Q為 S、Se、Te、NH或 Νϋ ;以及 T在每次出現時為相同或不同且係選自 S、NR6、〇、SiR62、Se、Te與 PR6 ; γ為 Ν ; R6為Η、D或院基；以及至少有一氘。該稠合多環雜芳族單體可進一步經基團所取代，該基團係選***基、雜烧基、醇、苄基、羧酸鹽、醚、醚羧酸鹽、醚磺酸鹽、醋磺酸鹽、胺甲酸乙酯與上述物質的氘化類似物。在某些實施例中，該取代基基團為完全氘化。在某些貝細例中，S亥取代基基團為氟化。在某些實施例中， θ亥取代基基團為完全氣化。在某些實施例中，言玄帛合多環雜芳族翠體為一&化之嗟吩并（噻吩）。此類化合物之非氘化類似物已於如 MaC_〇leCules，34, 5746_5747 (2〇〇1);與心麵心⑶㈣ 35’ 72817286 (2002)中論及。在某些實施例中，該噻吩并 (嘆吩）係選自。塞吩并（2,3_b)。塞吩、。塞吩并（3,2仲塞吩盘嗟吩并塞吩’各可具有"個氣原子。在某些實施例中，該嗔吩并陶單體係進一步經至少一基團所取代，該基團係選自燒基、雜院基、醇、节基、缓酸鹽、醚、謎羧酸鹽、醚磺酸鹽、醋磺酸鹽、月安甲酸乙雖與上氘化類似物。在某些實施例中，該取代基基團為完全氘化。在某些實施例中’該取代基基團為氟化。在某些實施例中’該取代基基團為完全氟化。 I45486.doc -21 - 201127895 在某些實施例中，預料可用於在該新複合分散液中形成該聚合物的多環雜芳族單體包含式VI :145486.doc -20- 201127895 wherein: Q is S, Se, Te, NH or Νϋ; and T is the same or different at each occurrence and is selected from the group consisting of S, NR6, 〇, SiR62, Se, Te and PR6; γ is Ν; R6 is Η, D or 院; and at least one 氘. The fused polycyclic heteroaromatic monomer may be further substituted with a group selected from the group consisting of an alkyl group, a heteroalkyl group, an alcohol, a benzyl group, a carboxylate, an ether, an ether carboxylate, and an ether sulfonic acid. Salt, vinegar sulfonate, ethyl urethane and deuterated analogs of the above. In certain embodiments, the substituent group is fully deuterated. In some of the fine examples, the S substituent group is fluorinated. In certain embodiments, the θH substituent group is fully vaporized. In certain embodiments, the polycyclic heteroaromatic genus is an & phenanthrene (thiophene). Non-deuterated analogs of such compounds are described, for example, in MaC_〇leCules, 34, 5746_5747 (2〇〇1); and in the face center (3) (4) 35' 72817286 (2002). In certain embodiments, the thieno (excitation) is selected from the group consisting of. The phenotype (2,3_b). Sai,. The phenophene (3,2 sec- sec- phenophene exemplified) may each have a gas atom. In certain embodiments, the porphindol system is further substituted with at least one group, The group is selected from the group consisting of a burnt base, a miscellaneous base, an alcohol, a sulfhydryl group, a buffer acid salt, an ether, a carboxylic acid salt, an ether sulfonate, a vinegar sulfonate, and a benzoic acid In certain embodiments, the substituent group is fully deuterated. In certain embodiments, the substituent group is fluorinated. In certain embodiments, the substituent group is fully fluorinated. I45486.doc -21 - 201127895 In certain embodiments, a polycyclic heteroaromatic monomer that is expected to be useful in forming the polymer in the new composite dispersion comprises Formula VI:

其中： Q 為 S、Se、Te或NR6 ; T 係選自 s、NR6、〇、siR62、Se、Te 與 PR6 ; E係選自伸烯基、伸芳基與雜伸芳基； R2為氫或氘； R6為氫、氛或烧基； R13在每次出現時為相同或不同，並且係選自由氫、氘、烷基、烯基、烷氧基、烷醯基、烷硫基、芳氧基、烷硫烷基、烷芳基、芳烷基、胺基、烷胺基、二烷胺基、芳基、烷亞磺醯基、烷氧烷基、烷磺醯基、芳硫基、芳亞磺醯基、烷氧羰基、芳磺醯基、丙嫌酸、鱗酸、膦醅、忐去、以》Wherein: Q is S, Se, Te or NR6; T is selected from the group consisting of s, NR6, 〇, siR62, Se, Te and PR6; E is selected from the group consisting of an alkenyl group, an aryl group and a heteroaryl group; Or 氘; R6 is hydrogen, aryl or alkyl; R13 is the same or different at each occurrence, and is selected from the group consisting of hydrogen, hydrazine, alkyl, alkenyl, alkoxy, alkyl fluorenyl, alkylthio, aryl Oxyl, alkylthioalkyl, alkaryl, aralkyl, amine, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkanesulfonyl, arylthio , arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, squaric acid, phosphinium, hydrazine, to

3、4、5、6或7員芳環或脂環，該環可選擇性地包 145486.doc •22· 201127895 括-或多個之二價氮、硫、硒、碲或氧原子。在某些實施例中，該導電聚合物為-先質單體與至少-第二單體之共聚合物。可使用任何種類之第- Λ ^ 弟一早體，只要其不會對該共聚合物之所欲性質產生不利影響。在某些實施例中，該第二單體匕3不超過50%的该聚合物，此比例係基於單體單元之總數。在某些實施例中，該第二單體包含不超過30%，此比例係基於單體單元之總數。在某些實施例中，該第二單體包含不超過10%，此比例係基於單體單元之總數。第二單體之示例性種類包括但不限於烯基、炔基、伸芳基、雜伸芳基與上述物質的仇化類似物。第二單二之實例包括但不限於i H(GXadiazGle)H、苯并Β塞二唑、伸苯伸乙烯基（phenylenevinylene)、伸苯伸乙快基 (phenyieneethynylene)、吡啶、二畊（diazin以）、三口井 (tdazines)與上述物質之氘化類似物，以上所有皆可進一步經取代。在某些實施 <列中，係、藉由先形成一中間體先質單體而製成該共聚合物，該中間體先質單體具有結構A b_c，其中 A與C代表可為相同或不同之先質單體，而B代表一第二單體。可使用標準的有機合成技術製備該A_B_C中間體先質單體’該等有機合成技術例*Yamam〇t〇、StiUe、㈤糾㈣ metathesis、suzuki&Negishi耦合法。而後藉由單獨氧化聚合該中間體先質單體，或者與一或多之額外先質單體氧化聚合而形成該共聚合物。 145486.doc -23- 201127895 在某些實施例中該導電聚合物係選自由__ 氘化聚噻吩、一氘化聚苯胺、一氘化聚吡咯、一氘化聚合性稠合多環雜芳族、一氘化聚（胺基吲哚）、一上述物質之共聚I物以及上述物質之組合所組成之群組。在某些實施例中’該導電聚合物係選自由聚（〇6_ EDOT)、聚（D5-Py)、聚（D7-ani)、聚（全氘I胺基十朵6) (p〇ly(perdeuter〇-4-aminoindole))、聚（全氘胺基巧丨 d朵）、聚（全氘-噻吩并（2,3-b)噻吩）、聚（全氘_噻吩并（3,2_b)噻吩）與聚（全氣塞吩并（3,4-b)°塞吩）》 3·高度氟化之酸聚合物該高度氟化之酸聚合物（「HFAP」）可為任何高度氟化且具酸性基團之聚合物。該酸性基團供應一可離子化之質子 (H+)或氘核（D+)。在某些實施例中，該酸性基團之pKa小於3。在某些實施例中，該酸性基團之pKa小於〇。在某此實施例中，該酸性基團之pKa小於該酸性基團可直接連接於該聚合物之主鏈，或連接於該聚合物主鏈上之側鏈。酸性基團的實例包括但不限於羧酸基團、磺酸基團、磺醯亞胺基團、磷酸基團、膦酸基團及上述物質之組合。 5亥些酸性基團可為全部相同，或者該聚合物可具有多於一種的酸性基團。在某些實施例中，該酸性基團係選自由績酸基團、磺醯亞胺基團及上述物質之組合所組成之群組。在某些實施例中，該HFAP為一具有酸性氘核之氘化酸 (deutero-acid) 〇在某些實施例中，該HFAP係至少95¾經氟化；在某些實 145486.doc -24- 201127895 施例中，為完全氟化。在某些實施例中，當該HFAp為未凡全氟化時’該些非氟化之位點係氘化而無氫存在。在某二實把例中，該HFAP為完全氟化並且為一具有酸性氛核之氘化酸。在某些實施例中，該HFAP為具水溶性。在某些實施例中’該HFAP可分散於水中。在某些實施例巾，該HFAp為 • I有機溶劑可濕性。術語「具有機溶劑可濕性」係指一材 ' 料在形成為一膜時，該膜與有機溶劑形成之接觸角不大於 60 C 。在某些實施例中，可濕性材料形成苯己烷 (Phenylhexane)可濕的膜並且其接觸角不大於乃。。測量= 觸角之方法係為熟知技術。在某些實施例中，該可濕性材料可由一聚合性酸所製成，該酸本身非具可濕性，但與選擇性的添加劑結合可使其具可濕性。合適的聚合性主鏈實例包括但不限於聚烯烴、聚丙烯酸醋、聚甲基丙烯酸g旨、聚酸亞胺、聚醯胺、&芳酿胺、聚丙烯醯胺、聚苯乙烯、上述物質之共聚合物或上述物質2 • ^匕類似物’以上所有皆為高度氟化；在某些實施例中之 . 為完全氣化。在一實施例中，該酸性基團為磺酸基團或磺醯亞胺基團。一磺醯亞胺基團具有式：. 1A 3, 4, 5, 6 or 7 member aromatic ring or alicyclic ring, which may optionally include 145486.doc • 22· 201127895 including or a plurality of divalent nitrogen, sulfur, selenium, tellurium or oxygen atoms. In certain embodiments, the conductive polymer is a copolymer of a precursor monomer and at least a second monomer. Any type of first- Λ 一早早早。。。。。。。。。。。。。。。。。。。。。。 In certain embodiments, the second monomer 匕3 does not exceed 50% of the polymer, and the ratio is based on the total number of monomer units. In certain embodiments, the second monomer comprises no more than 30%, based on the total number of monomer units. In certain embodiments, the second monomer comprises no more than 10% based on the total number of monomer units. Exemplary classes of second monomers include, but are not limited to, alkenyl, alkynyl, extended aryl, heteromeric aryl groups and enzymatic analogs of the foregoing. Examples of the second single includes, but are not limited to, i H (GXadiazGle) H, benzoxadiazole, phenylenevinylene, phenyieneethynylene, pyridine, diplise (diazin ), three wells (tdazines) and deuterated analogs of the above substances, all of which may be further substituted. In certain embodiments, the copolymer is prepared by first forming an intermediate precursor monomer having a structure A b — c, wherein A and C represent the same Or different precursor monomers, and B represents a second monomer. The A_B_C intermediate precursor monomer can be prepared using standard organic synthesis techniques. These organic synthesis techniques are: Yamam〇t〇, StiUe, (5) Correction (4) metathesis, suzuki & Negishi coupling method. The intermediate is then polymerized by oxidative polymerization alone or by oxidative polymerization with one or more additional precursor monomers. 145486.doc -23- 201127895 In certain embodiments, the electrically conductive polymer is selected from the group consisting of __ deuterated polythiophene, mono-deuterated polyaniline, mono-deuterated polypyrrole, mono-deuterated polymeric fused polycyclic heteroaryl A group consisting of a group, a poly(aminoguanidine), a copolymerized substance of the above substance, and a combination of the above. In certain embodiments, the conductive polymer is selected from the group consisting of poly(〇6_EDOT), poly(D5-Py), poly(D7-ani), poly(full 氘I amine based on 10) (p〇ly (perdeuter〇-4-aminoindole)), poly(full amide-based 丨), poly(p-indole-thieno(2,3-b)thiophene), poly(full 氘_thieno (3,2_b) ) thiophene) and poly(full gas pheno (3,4-b) ° phenophene) 3. Highly fluorinated acid polymer The highly fluorinated acid polymer ("HFAP") can be any highly fluorine A polymer having an acidic group. The acidic group supplies an ionizable proton (H+) or a deuteron nucleus (D+). In certain embodiments, the acidic group has a pKa of less than 3. In certain embodiments, the acidic group has a pKa less than 〇. In one such embodiment, the acidic group has a pKa less than the acidic group which may be attached directly to the backbone of the polymer or to a side chain of the polymer backbone. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations of the foregoing. The acidic groups may be all the same, or the polymer may have more than one acidic group. In certain embodiments, the acidic group is selected from the group consisting of a C6 group, a sulfonimide group, and combinations of the foregoing. In certain embodiments, the HFAP is a deutero-acid having an acidic deuteron nucleus. In certain embodiments, the HFAP is at least 953⁄4 fluorinated; in some 145486.doc -24 - 201127895 In the example, it is completely fluorinated. In certain embodiments, when the HFAp is unusually perfluorinated, the non-fluorinated sites are deuterated without hydrogen. In a second embodiment, the HFAP is fully fluorinated and is a deuterated acid having an acidic nucleus. In certain embodiments, the HFAP is water soluble. In certain embodiments, the HFAP can be dispersed in water. In certain embodiments, the HFAp is • I organic solvent wettability. The term "having organic solvent wettability" means that when a material is formed into a film, the film forms a contact angle with the organic solvent of not more than 60 C. In certain embodiments, the wettable material forms a wettable film of Phenylhexane and has a contact angle no greater than. . The method of measuring = antenna is a well-known technique. In certain embodiments, the wettable material can be made from a polymeric acid that is not inherently wettable, but which, in combination with a selective additive, renders it wettable. Examples of suitable polymeric backbones include, but are not limited to, polyolefins, polyacrylic acid vinegar, polymethacrylic acid, polyimide, polyamine, & arylamine, polyacrylamide, polystyrene, The co-polymer of the substance or the above-mentioned substance 2 ^ ^ 匕 analog 'all of the above are highly fluorinated; in some embodiments, it is completely vaporized. In one embodiment, the acidic group is a sulfonic acid group or a sulfonimide group. The sulfonimide group has the formula:

-S〇2-NH-S02-R 其中R為一烷基基團。一氘化-磺醯亞胺基團具有弋.-S〇2-NH-S02-R wherein R is an alkyl group. A mono-sulfonimide group has a hydrazine.

-S〇2-ND-S〇2-R 其中R為一烷基基團。 145486.doc -25- 201127895 在一實施例中’該酸性基團係位於一氟化側鏈上。在某些實施例中’該氟化側鏈係選自烷基基團、院氧基基圏、胺基基團、***基團及上述物質之組合，以上所有皆完全氟化。在一實施例中，該HFAP具有一高度氟化之烯烴主鏈，並具有側支（pendant)的高度氟化之烷基磺酸鹽、高度氣化之醚磺酸鹽、高度氟化之酯磺酸鹽或高度氟化之醚續醯亞胺基團。在一實施例中’該HFAP為一具有全氟_醚_確酸側鏈之全氟烯烴。在一實施例中，該聚合物為1，1-二氟乙稀及2-(1，1-二氟-2-(三氟甲基）烯丙氧基四氟乙烷橫酸的共聚合物。在一實施例中，該聚合物為乙烯及2-(2-(1，2,2-三氟乙烯氧基）-1，1，2,3,3,3-六氟丙氧基2_四氟乙蟥酸的共聚合物。這些共聚合物可製成為對應之碌醯氟聚合物，而後可轉化成磺酸形式。在一實施例中，該HFAP為一氟化與部分磺化之聚（伸芳基醚；ε風）（poly(arylene ether sulfone))的同元聚合物或共聚合物。該共聚合物可為一團聯共聚合物（block copolymer)。在一實施例中，該HFAP為一磺醯亞胺聚合物，其具有式IX :-S〇2-ND-S〇2-R wherein R is an alkyl group. 145486.doc -25- 201127895 In one embodiment, the acidic group is located on a fluorinated side chain. In some embodiments, the fluorinated side chain is selected from the group consisting of an alkyl group, an alkoxy group, an amine group, an ether group, and combinations of the foregoing, all of which are fully fluorinated. In one embodiment, the HFAP has a highly fluorinated olefin backbone and has a pendant highly fluorinated alkyl sulfonate, a highly vaporized ether sulfonate, a highly fluorinated ester. A sulfonate or a highly fluorinated ether continuation of the imine group. In one embodiment, the HFAP is a perfluoroolefin having a perfluoro-ether-acid side chain. In one embodiment, the polymer is a copolymer of 1,1-difluoroethylene and 2-(1,1-difluoro-2-(trifluoromethyl)allyloxytetrafluoroethane cross-acid. In one embodiment, the polymer is ethylene and 2-(2-(1,2,2-trifluoroethyleneoxy)-1,1,2,3,3,3-hexafluoropropoxy a copolymer of 2_tetrafluoroacetic acid. These copolymers can be made into the corresponding fluoropolymer and then converted to the sulfonic acid form. In one embodiment, the HFAP is monofluorinated and partially sulfonated. A homopolymer or copolymer of poly(arylene ether sulfone). The copolymer may be a block copolymer. In one embodiment, the HFAP is a sulfonimide polymer having the formula IX:

其中： 145486.doc -26- 201127895 R2為Η或D ;Where: 145486.doc -26- 201127895 R2 is Η or D;

Rf㈣^高度氟化之伸烧基、高度l化之雜伸烧基、 Γ7度氟化之伸芳基與高度氟化之雜伸芳基，其可為經一或多個之醚氧所取代；以及 η 至少為4。在式IX的-實施例中’ Rf為一全氟烷基基團。在一實施例中，〜為-全氟丁基基團。在―實施例t，&含有喊氧。在一貫施例中，η為大於1 〇。在-實施例中，該HFAP包含-高度氟化之聚合物主鍵與一側鏈，該側鏈具有式X : OR15-S02-N-(S〇2-N-S〇2-N)a-S02R16 (X)Rf(tetra)|highly fluorinated stretching group, highly fused hetero-alkyl group, 7-degree fluorinated aryl group and highly fluorinated heteroaryl group, which may be substituted by one or more ether oxygens ; and η is at least 4. In the embodiment of formula IX, 'Rf is a perfluoroalkyl group. In one embodiment, ~ is a perfluorobutyl group. In the embodiment t, & contains oxygen. In the consistent example, η is greater than 1 〇. In an embodiment, the HFAP comprises a highly fluorinated polymer primary bond and a side chain having the formula X: OR15-S02-N-(S〇2-NS〇2-N)a-S02R16 ( X)

• I I• I I

D D D 其中： R15為一高度氟化之伸烷基基團或一高度氟化之雜伸貌基基團； R16為一高度氟化之烷基或一高度氟化之芳基基團；以及 a 為0或1至4的整數。在一實施例中，該HFAP具有式XI : ——(CF2-CF2)c-(CF2-CF)—— η (XI) . Ο」 (CF2-CF-0)c-(CF2)c~S〇2-N~(S〇2-(CF2)c-S〇2-N)c*'S〇2f^i6 145486.doc -27- 201127895 其中： R16為一高度氟化之烷基或一高度氟化之芳基基團； c獨立為0或一 1至3的整數；並且 η 至少為4。該HFAPs之非氘化類似物的合成已描述於如A. Feiring et al·，J. Fluorine Chemistry 2000，105，129-135 ; A. Feiring et al.，Macromolecules 2000，33，9262-9271 ； D. D. D. Desmarteau luorine Chem. 1995，72，203-208 ； A J.DDD wherein: R15 is a highly fluorinated alkylene group or a highly fluorinated heterophenyl group; R16 is a highly fluorinated alkyl group or a highly fluorinated aryl group; Is an integer of 0 or 1 to 4. In one embodiment, the HFAP has the formula XI: - (CF2-CF2)c-(CF2-CF) - η (XI) . Ο" (CF2-CF-0)c-(CF2)c~S 〇2-N~(S〇2-(CF2)cS〇2-N)c*'S〇2f^i6 145486.doc -27- 201127895 where: R16 is a highly fluorinated alkyl group or a highly fluorinated An aryl group; c is independently 0 or an integer from 1 to 3; and η is at least 4. The synthesis of non-deuterated analogs of such HFAPs has been described, for example, in A. Feiring et al., J. Fluorine Chemistry 2000, 105, 129-135; A. Feiring et al., Macromolecules 2000, 33, 9262-9271; DDD Desmarteau luorine Chem. 1995, 72, 203-208; A J.

Appleby et al·，J. Electrochem. Soc. 1993，14〇(i)，i〇9_ 111 ;以及Desmarteau之美國專利第5,463,005號中。在一貫細例中’ δ亥HFAP亦包含一重複單元，該重複單元係衍生自至少一高度氟化之乙烯化不飽和（ethylenicaUy imsaturated)化合物。該全氟烯烴包含2至2〇個碳原子。代表性之全說烯烴包括但不限於四氟乙烯、六氟丙烯、全氟-(2,2-二甲基-l，3-二咩唑 ^ 、全氟_(2_ 亞甲基_4_ 甲基_13 二口号c)(perfiu__’(2- methylene-4-methyl-l，3-di〇x〇lane))、CF2=CF〇(CF2)tCF=CF2，其中t為i或2，並且Rf，，0CF = CF2，其中Rf"為一具有ι至約^ 個碳原子的飽和全氧烧基基團。在—實施例中，該共聚單體為四.氟乙烯。在一實施例中，該HFAP為—膠體形成之聚合性酸。如本文中所用者，術語「膠體形成」係指不溶於水之材料，並且在分散至一水性介質時會形成膠體。該膠體形成聚合性酸通常具有分子量範圍為約i〇，_至約4，刪，綱。在一 145486.doc -28· 201127895Appleby et al., J. Electrochem. Soc. 1993, 14(i), i 〇 9_111; and Desmarteau, U.S. Patent No. 5,463,005. In the conventional example, δHai HFAP also contains a repeating unit derived from at least one highly fluorinated ethylenica Uy imsaturated compound. The perfluoroolefin contains 2 to 2 carbon atoms. Representative olefins include, but are not limited to, tetrafluoroethylene, hexafluoropropylene, perfluoro-(2,2-dimethyl-l,3-dicarbazole^, perfluoro-(2_methylene_4_A) Base_13 two slogans c) (perfiu__'(2- methylene-4-methyl-l,3-di〇x〇lane)), CF2=CF〇(CF2)tCF=CF2, where t is i or 2, and Rf,, 0CF = CF2, wherein Rf" is a saturated oxyalkylene group having from 1 to about carbon atoms. In an embodiment, the comonomer is tetrafluoroethylene. In one embodiment The HFAP is a colloid-forming polymeric acid. As used herein, the term "colloidal formation" means a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. The colloid forms a polymeric acid. Having a molecular weight in the range of about i 〇, _ to about 4, deleted, syllabic. In a 145486.doc -28· 201127895

式，如下所述。子量為約1〇〇,〇〇〇至約匕2奈米（nm)至約14〇 ηιη。 nm至約30 nm。可使用 '體形成聚合性材料。上文 ^性形式’例如鹽、酯或磺以製備導電組成物之酸形在某些實施例中， HFAP包括一高度氟化之碳主鏈及側鏈，其由下式表示：Formula, as described below. The amount is about 1 Torr and is about 匕2 nm (nm) to about 14 〇 ηιη. Nm to about 30 nm. A 'body-forming polymerizable material can be used. The above-described "sexual form" such as a salt, ester or sulfonate to form an acid form of a conductive composition. In certain embodiments, the HFAP comprises a highly fluorinated carbon backbone and a side chain, which is represented by the formula:

在某些實施例中，該HFAP可為揭示於美國專利第 3,282,875號與美國專利第4,358,545與4,940,525號中之聚合物。在某些實施例中，該HFAP包含一全氟碳主鏈以及側鏈’其由式-0-CF2CF(CF3)-0-CF2CF2S03E5所表示其中 E5定義如上。此類HFAP係揭示於美國專利第3,282,875號並且可藉由下列程序而製成，包括转聚合四氟乙烯（TFE) 與該全氟化之乙烯醚 CF2=CF-0-CF2CF(CF3)-〇-CF2CF2S〇2F , 全氟（3,6-二氧-4-甲基-7-辛烯磺醯氟）（PDMOF)，接著藉由水解該績醯氟基團而轉化為續酸鹽基團，並且進行必要的離子交換而將其轉化為所欲之離子形式。揭示於美國專利案第4,358,545號及第4,940,525號之該類聚合物的實例具有 M5486.doc .29- 201127895 側鏈-0-CF2CF2S03E5，其中E5係定義如上。此聚合物可藉由下列程序而製成，包括共聚合四氟乙烯（TFE)和全氟化之乙烯醚CF2=CF-0-CF2CF2S02F，全氟（3-氧-4-辛烯磺醯氟）（POPF)，接著藉由水解及進行進一步必要的離子交換。一種市售可得的HFAP為水性Nafion®分散液，來自E·I· du Pont de Nemours and Company (Wilmington，DE)。該氘化酸可由該質子性HFAP所製成，此係藉由分離該固體酸材料並在d2o中於加溫加壓條件下進行。在某些實施例中，該固體HFAP係在D20中加熱至100至300°C間之溫度（於一密閉加壓容器中）。 4.導電組成物該新的導電組成物包含： (1) 一組成物，其包含一氘化之導電聚合物，該聚合物摻雜一高度氟化之酸聚合物；或者 (2 ) —組成物，其包含： (a) —氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸；以及 (b) 至少一高度氟化之酸聚合物。在某些實施例中，一導電組成物包含（a) —氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸以及（b)—高度氟化之酸聚合物。在某些實施例中，一導電組成物主要由（a) 一氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸以及（b) —高度氟化之酸聚合物所構成。 145486.doc -30- 201127895 在某些實施例中，一導電組成物包含一氘化之導電聚合物，該聚合物摻雜一高度氟化之酸聚合物。在某些實施例中，一導電組成物主要由一氘化之導電聚合物所構成，該聚合物摻雜一高度氟化之酸聚合物。在某些實施例中，一導電組成物包含： (1) 一液體組成物，其包含 (a) 至少一氘化之導電聚合物，該聚合物換雜至少—高度氟化之酸聚合物；以及 (b) —氘化之液體介質；或者 (2) —液體組成物，其包含 (a)至少一氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸； (b) 至少一高度氟化之酸聚合物；以及 (c) 一氘化之液體介質。导敗組成物包含―氣化之液體介在某些實施例中質，於其中分散有⑷—沉化之導電聚合物，該聚合物換雜 -非氟化之聚合性酸以及⑻-高度氟化之酸聚合物。在某些實施例中，一導電組成物包含一 D2〇，於其中分散有⑷ -氛化之導電聚合物，該聚合物摻雜—非氟化之聚合性酸以及㈨-高度氟化之酸聚合物。在某些實施例中，—導電組成物主要由一氘化之液體介質所 — 再成於其中分散有（a)In certain embodiments, the HFAP can be a polymer disclosed in U.S. Patent No. 3,282,875 and U.S. Patent Nos. 4,358,545 and 4,940,525. In certain embodiments, the HFAP comprises a perfluorocarbon backbone and a side chain 'which is represented by the formula -0-CF2CF(CF3)-0-CF2CF2S03E5 wherein E5 is as defined above. Such HFAP is disclosed in U.S. Patent No. 3,282,875 and may be made by the following procedures, including transpolymerization of tetrafluoroethylene (TFE) with the perfluorinated vinyl ether CF2=CF-0-CF2CF(CF3)-〇. -CF2CF2S〇2F, perfluoro(3,6-dioxo-4-methyl-7-octenesulfonylfluoro) (PDMOF), which is then converted to a sulphonate group by hydrolysis of the fluorinated fluoro group And carry out the necessary ion exchange to convert it into the desired ionic form. Examples of such polymers disclosed in U.S. Patent Nos. 4,358,545 and 4,940,525 have M5486.doc.29-201127895 side chain-0-CF2CF2S03E5, wherein E5 is as defined above. The polymer can be prepared by the following procedures, including copolymerization of tetrafluoroethylene (TFE) and perfluorinated vinyl ether CF2=CF-0-CF2CF2S02F, perfluoro(3-oxo-4-octenesulfonate fluoride) (POPF), followed by hydrolysis and further necessary ion exchange. One commercially available HFAP is an aqueous Nafion® dispersion from E. I. du Pont de Nemours and Company (Wilmington, DE). The deuterated acid can be produced by the proton HFAP by separating the solid acid material and performing the heating under pressure in d2o. In certain embodiments, the solid HFAP is heated in D20 to a temperature between 100 and 300 ° C (in a closed pressurized container). 4. Conductive Composition The novel conductive composition comprises: (1) a composition comprising a deuterated conductive polymer doped with a highly fluorinated acid polymer; or (2) - composition And comprising: (a) a deuterated electrically conductive polymer doped with a non-fluorinated polymeric acid; and (b) at least one highly fluorinated acid polymer. In certain embodiments, a conductive composition comprises (a) a deuterated conductive polymer doped with a non-fluorinated polymeric acid and (b) a highly fluorinated acid polymer. In certain embodiments, a conductive composition consists essentially of (a) a deuterated conductive polymer doped with a non-fluorinated polymeric acid and (b) a highly fluorinated acid polymer. Composition. 145486.doc -30- 201127895 In certain embodiments, a conductive composition comprises a deuterated electrically conductive polymer doped with a highly fluorinated acid polymer. In certain embodiments, a conductive composition consists essentially of a deuterated conductive polymer doped with a highly fluorinated acid polymer. In certain embodiments, a conductive composition comprises: (1) a liquid composition comprising (a) at least one deuterated electrically conductive polymer, the polymer being modified to at least a highly fluorinated acid polymer; And (b) a liquid medium that is deuterated; or (2) a liquid composition comprising (a) at least one deuterated electrically conductive polymer doped with a non-fluorinated polymeric acid; At least one highly fluorinated acid polymer; and (c) a deuterated liquid medium. The destructive composition comprises a "vaporized liquid" which, in certain embodiments, is dispersed in a (4)-thinned conductive polymer, the polymer is modified-non-fluorinated polymeric acid and (8)-highly fluorinated Acid polymer. In certain embodiments, a conductive composition comprises a D2 crucible in which a (4)-incorporated conductive polymer is dispersed, the polymer is doped - a non-fluorinated polymeric acid and (9) a highly fluorinated acid polymer. In some embodiments, the electrically conductive composition is primarily comprised of a deuterated liquid medium - and dispersed therein (a)

一爪化之導電聚合物，該聚合物摻雜^ VL 非既化之聚合性酸以及（b)m化之酸聚合物。在某些實_中，__ 組成物主要由一D20所構成，於其％ T刀政有（a)—氘化之導 145486.doc •31 · 201127895 電：合物，該聚合物摻雜—非氟化之聚合性酸以及㈨一高度氟化之酸聚合物所構成。在某些實㈣中，—導電組成物包含—乱化之液體介 f於其中刀散有-爪化之導電聚合物，該聚合物播雜一尚度氟化之酸聚合物。在笨此杳在某些實施例中，—導電組成物包含-帥，於其中分散有—氣化之導電聚合物，該聚合物摻雜-局度氟化之酸聚合物。在某些實施例中，該導電组成物主要由-氣化之液體介質所構成，於其中分散有一氣化之導電聚合物’該聚合物摻雜一高度氣化之酸聚合物。在某些實施例巾，該導電組成物主要由DA所構成，於盆中分散有⑷-氖化之導電聚合物，該聚合物摻雜一高度氟化之酸聚合物。在某些實施例中’選擇性之添加劑係存在於該組成物中。可添加之材料類型的實例包括但不限於聚合物、染料、塗布助劑、有機及無機導電墨水和糊膠、電荷傳輸材料、父聯劑及上述物質之組合。該添加劑應為可溶於或分散於該氘化之液體介質中的材料並且可為簡單分子或聚合物。 a.摻雜一非氟化之聚合性酸的氘化之導電聚合物任何能夠摻雜該導電聚合物的非氟化之聚合性酸皆可用以製成該新的複合分散液。在某些實施例中，該非氟化之聚合性酸為低於10%經氟化；在某些實施例中，為低於1% 經氣化。在某些實施例中，該非氟化之聚合性酸不具有氟。在某些實施例中，該非氟化之聚合性酸為一氘化酸。 145486.doc -32- 201127895 在某些實施例中，該非氟化之氘化酸係至少10%經氘化；在某些實施例中，至少20%經氘化；在某些實施例中，至少30%經氘化；在某些實施例中，至少4〇%經氘化；在某些貫細•例中，至少50%經氘化；在某些實施例中，至少 60%經氘化，在某些實施例中，至少7〇%經氘化；在某些貫施例中，至少80%經氘化；在某些實施例中，至少卯％經氘化。在某些實施例中’該非氟化之氘化酸為1〇〇%經氘化。二酸性基團之實例包括但不限於羧酸基團、磺酸基團、磺醯亞胺基團、磷酸基團、膦酸基團、上述物質之氣化類似物與上述物質之組合。該些酸性團基可為全部相同或者該聚合物可具有多於一種的酸性基團。在實施例中，s純為一非氣化之聚合性續酸。該些酸之某些非限定實例為聚（苯乙稀石黃酸）（「psSA」）、聚(全気-苯乙料酸）（「D8-PSSA」）、聚（2丙稀醯胺_2_甲基丙績酸K「_PSA」）、聚(全說_2_丙稀醯胺_2_子基_ i 丙石黃酸）（「Dl3-PAAMPSA」）與上述物質之混合物。非氟化之4 口性^存在的量，通常會超過抵消該導電聚合物電荷所需的量。在某些實施例中，非氟化之聚合性酸的酸當量與導電聚合物之莫耳當量的比例範圍為、該經摻雜之導電聚合物可藉由氧化聚合該先質單體而形成，此聚合係於該非氟化之聚合性酸（在⑽中）存在下進類單體之氧化a合係為熟知技術。可使用氧化劑如過硫酸鈉或過硫酸鉀。在某些情況下，亦可使用―催化劑 145486.doc -33 - 201127895 如硫酸鐵。所得產物為該氘化之導電聚合物在d2o中的分散液，該聚合物摻雜該非氟化之聚合性酸。在某些實施例中，該經掺雜之導電聚合物係選自由摻雜 D8-PSSA 之聚（D6-EDOT)、摻雜 D8-PSSA 之聚（D5-Py)與摻雜D13-PAAMPSAiD7-Pani所組成之群組。這些導電聚合物係縮寫為聚（D6-EDOT)/D8-PSSA、聚（D5-Py)/D8-PSSA與 Dy-Pani/D13_PAAMPSA。在以下討論中，該氘化之導電聚合物與HFAP皆以單數表示。然而，應理解所使用之上述其一或兩者可多於一個。該導電組成物的製備係藉由先形成該氘化且經摻雜之導電聚合物，而後以任何順序添加該HFAP與選擇性之添加劑。HFAP之酸當量與非氟化摻雜酸之酸當量的比例至少為0.1，並且不大於4;在某些實施例中，不大於2。該氘化且經摻雜之導電聚合物的形成通常藉由氧化聚合一氘化之先質單體，此聚合係在該非氟化之聚合性酸（在一氘化之液體介質中）存在下進行。該氘化之液體介質通常為D20或者D20與全氘化之有機溶劑的一混合物。許多這些材料皆為市售可得。該HFAP可先溶於或分散於該氘化之液體介質中。此物而後可添加至該氘化之導電聚合物在一氘化之液體介質中的一分散液中。當該選擇性之添加劑存在時，該添加劑可於任何時點添加。該添加劑可以溶液或分散液（在一氘化之液體介質中） 145486.doc -34· 201127895 ^ 的形式添加，或者其可直接以固體的形式添加。A clawed conductive polymer doped with a VL non-conforming polymeric acid and (b) an acidified acid polymer. In some real _, the __ composition is mainly composed of a D20, in which the % T knife has (a) - 氘化的导145486.doc • 31 · 201127895 electric: compound, the polymer doping - A non-fluorinated polymeric acid and (9) a highly fluorinated acid polymer. In some embodiments (4), the electrically conductive composition comprises - a corroded liquid polymer in which the knife is dispersed with a claw-shaped conductive polymer, the polymer is doped with a fluorinated acid polymer. In some embodiments, the electrically conductive composition comprises - handsome, in which a vaporized electrically conductive polymer is dispersed, the polymer being doped with a partially fluorinated acid polymer. In certain embodiments, the electrically conductive composition consists essentially of a vaporized liquid medium having a vaporized electrically conductive polymer dispersed therein. The polymer is doped with a highly vaporized acid polymer. In some embodiments, the conductive composition consists essentially of DA in which a (4)-deuterated conductive polymer is dispersed, the polymer being doped with a highly fluorinated acid polymer. In certain embodiments, a 'selective additive is present in the composition. Examples of types of materials that may be added include, but are not limited to, polymers, dyes, coating aids, organic and inorganic conductive inks and pastes, charge transport materials, parent binders, and combinations thereof. The additive should be a material that is soluble or dispersible in the deuterated liquid medium and can be a simple molecule or polymer. a. Conductive polymer doped with a non-fluorinated polymeric acid Any non-fluorinated polymeric acid capable of doping the conductive polymer can be used to make the new composite dispersion. In certain embodiments, the non-fluorinated polymeric acid is less than 10% fluorinated; in certain embodiments, less than 1% is vaporized. In certain embodiments, the non-fluorinated polymeric acid does not have fluorine. In certain embodiments, the non-fluorinated polymeric acid is a monoacid. 145486.doc -32- 201127895 In certain embodiments, the non-fluorinated acidified acid is at least 10% deuterated; in certain embodiments, at least 20% is deuterated; in certain embodiments, At least 30% is deuterated; in some embodiments, at least 4% is deuterated; in some embodiments, at least 50% is deuterated; in some embodiments, at least 60% is deuterated. In some embodiments, at least 7% is deuterated; in some embodiments, at least 80% is deuterated; in some embodiments, at least % is deuterated. In certain embodiments, the non-fluorinated bismuth acid is deuterated by 1%. Examples of the diacid group include, but are not limited to, a carboxylic acid group, a sulfonic acid group, a sulfonimide group, a phosphoric acid group, a phosphonic acid group, a vaporized analog of the above, and a combination thereof. The acidic groups may be all the same or the polymer may have more than one acidic group. In the examples, s is pure to a non-gasified polymeric acid. Some non-limiting examples of such acids are poly(styrene) ("psSA"), poly(p-phenylene acid) ("D8-PSSA"), poly(2-acrylamide) _2_Methylpropionic acid K "_PSA"), poly (all said _2_ acrylamide 2_subunit _ i propofin) ("Dl3-PAAMPSA") and a mixture of the above substances. The amount of non-fluorinated 4-position is usually greater than the amount required to counteract the charge of the conductive polymer. In certain embodiments, the ratio of the acid equivalent of the non-fluorinated polymeric acid to the molar equivalent of the conductive polymer ranges from that the doped conductive polymer can be formed by oxidative polymerization of the precursor monomer. This polymerization is a well-known technique for the oxidation of the monomer in the presence of the non-fluorinated polymeric acid (in (10)). An oxidizing agent such as sodium persulfate or potassium persulfate can be used. In some cases, it is also possible to use "catalyst 145486.doc -33 - 201127895 such as iron sulphate. The resulting product is a dispersion of the deuterated conductive polymer in d2o which is doped with the non-fluorinated polymeric acid. In certain embodiments, the doped conductive polymer is selected from the group consisting of poly(D6-EDOT) doped with D8-PSSA, poly(D5-Py) doped with D8-PSSA, and doped with D13-PAAMPSAiD7- A group of Pani. These conductive polymers are abbreviated as poly(D6-EDOT)/D8-PSSA, poly(D5-Py)/D8-PSSA and Dy-Pani/D13_PAAMPSA. In the following discussion, the deuterated conductive polymer and HFAP are all expressed in singular. However, it should be understood that one or both of the above may be used more than one. The conductive composition is prepared by first forming the deuterated and doped conductive polymer and then adding the HFAP and the optional additive in any order. The ratio of the acid equivalent of the HFAP to the acid equivalent of the non-fluorinated doped acid is at least 0.1 and not greater than 4; in some embodiments, not greater than 2. The formation of the deuterated and doped conductive polymer is usually carried out by oxidative polymerization of a precursor, which is in the presence of the non-fluorinated polymeric acid (in a deuterated liquid medium) get on. The deuterated liquid medium is typically a mixture of D20 or D20 with a fully deuterated organic solvent. Many of these materials are commercially available. The HFAP can be first dissolved or dispersed in the deuterated liquid medium. This material can then be added to a dispersion of the deuterated conductive polymer in a deuterated liquid medium. When the selective additive is present, the additive can be added at any point in time. The additive may be added in the form of a solution or dispersion (in a deuterated liquid medium) 145486.doc -34· 201127895 ^ or it may be added directly as a solid.

或者，可先形成該經摻雜之導電聚合物的非氘化類似物，接著再氘化該材料。在某些實施例中，一部分氘化之材料係經處理以增加氘化程度。氘化之方法係為熟知技術。氘化通常可藉由以氘化之溶劑（如d6-苯）處理該非氘化之化合物而達成，此係於一路易斯酸之Η/D交換催化劑（如三氯化鋁或氯化乙基鋁）或者酸如CF3COOD、DC1等存在下 . 進行。氘化方法之實例可發現於a)「Efficient H/DAlternatively, a non-deuterated analog of the doped conductive polymer can be formed first, followed by deuteration of the material. In some embodiments, a portion of the deuterated material is treated to increase the degree of deuteration. The method of deuteration is a well-known technique. Deuteration can usually be achieved by treating the non-deuterated compound with a deuterated solvent such as d6-benzene, which is a Lewis acid/D exchange catalyst such as aluminum trichloride or ethyl aluminum chloride. ) or acid in the presence of CF3COOD, DC1, etc.. An example of a deuteration method can be found in a) "Efficient H/D

Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd/C-H2-D20 System」 Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052-4063 ; b)「第 5、6族金屬鹵化物催化的芳香族化合物氫氚交換反應」郭巧霞、申寶劍、郭海卿與高橋保，中國化學，2005，23，341-344 (「Aromatic H/D Exchange Reaction Catalyzed by Groups 5 • and 6 Metal Chlorides」GUO, Qiao-Xia, SHEN，Bao-Jian; . GUO, Hai-Qing TAKAHASHI, Tamotsu Chinese Journal of 2005，23，341-344) ; c)「A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis(2,2'-bipyridine)iridium(III) ion 」Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd/C-H2-D20 System" Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052-4063; b) "Hydrogen exchange reaction of aromatic compounds catalyzed by Group 5 and 6 metal halides" Guo Qiaoxia, Shen Baojian, Guo Haiqing and Gao Qiaobao, Chinese Chemistry, 2005, 23, 341-344 ("Aromatic H/D Exchange Reaction Catalyzed by Groups 5 • and 6 Metal Chlorides” GUO, Qiao-Xia, SHEN, Bao-Jian; . GUO, Hai-Qing TAKAHASHI, Tamotsu Chinese Journal of 2005, 23, 341-344); c) "A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis(2,2'-bipyridine)iridium(III) ion ”

Richard J. Watts, Shlomo Efrima, and Horia Metiu J. Am. C/zem. 1979，101 (10)，2742-2743 ; d)「Efficient H-DRichard J. Watts, Shlomo Efrima, and Horia Metiu J. Am. C/zem. 1979,101 (10), 2742-2743 ; d) "Efficient H-D

Exchange of Aromatic Compounds in Near-Critical D20 145486.doc -35- 201127895Exchange of Aromatic Compounds in Near-Critical D20 145486.doc -35- 201127895

Catalysed by a Polymer-Supported Sulphonic Acid」CarmenCatalysed by a Polymer-Supported Sulphonic Acid" Carmen

Boix and Martyn Poliakoff Tetrahedron Letters 40 (1999) 4433.4436 ; e) US3849458; f)「Efficient C-H/C-DBoix and Martyn Poliakoff Tetrahedron Letters 40 (1999) 4433.4436 ; e) US3849458; f) "Efficient C-H/C-D

Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D20」HironaoExchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D20”Hironao

Sajiki，Fumiyo Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota 〇rS- Lett., 2004, 6 (9), 1485-1487 ° 在氘化該導電聚合物後’該HFAP與選擇性之添加劑係如上所述添加。在某些實施例中，在添加該選擇性添加劑之前或之後提高pH。該pH可藉由以氘化之陽離子交換樹脂與/或鹼性樹脂處理而調整。在某些實施例中’該PH係藉由添加一 D20 鹼性溶液而調整。用於該驗之陽離子可為但不限於鹼金屬、鹼土金屬、全氘-銨與全氘-烷基銨。在某些實施例中，鹼金屬優於鹼土金屬陽離子。可使用任何液相沉積技術由上述組成物製成膜，包括連續或非連續技術。連續沉積技術包括但不限於旋轉塗布、凹版塗布 '簾式塗亦、浸潰塗布、狹縫模具式塗布、喷灑塗布與連續喷嘴塗布。非連續沉積技術包括但不限於喷墨印刷、凹版印刷及網版印刷。從而形成之膜為連續、平滑且相對透明。 b.摻雜HFAP的氘化之導電聚合物在某些實施例中’該摻雜HFAP的氘化之導電聚合物係藉由氧化聚合該氘化之先質單體而形成，此聚合係在該 145486.doc •36- 201127895 HFAP(在一氘化之液體介質中）的存在下進行。在某些實施例中，耗化之液體介質為D2〇。該非氣化之類似物材料的聚合已描述於公開之美國專利申請案第2〇〇4/〇1〇2577、 2004/0127637與2005/0205860號中。所得產物為摻雜HFAp 的s亥级化之導電聚合物的一液體分散液。在某些實施例中，該組成物係選自由摻雜全氟化之氘化酸聚合物的聚（D4-ED0T)與聚（D6_ED〇T)、摻雜一全氟化之氘化酸聚合物的聚（Ds-Py)與摻雜一全氟化之氘化酸聚合物的DyPam所組成之群組。在某些實施例中，該全氟化之氣化酸聚合物為一 TFE(四氟乙烯）與PSEPVE(全氟_3,6·二氧_4-曱基-7-辛烯磺酸，其中該酸質子已交換為一氘核)之共聚合物。此材料係縮寫為「D_聚（TFE_pSEpvE)」。或者，可先形成該經摻雜之導電聚合物的非氘化類似物，接著再氖化該材料。在某些實施例中，—部分沉化之材料係經處理以增加氘化程度。氘化之方法係為熟知技術，如上所述。在某些貫她例中，係提高該分散液之pH，如上所述。經摻雜之導電聚合物的分散液在形成時約為2的邱至中性阳下仍維持穩定。在某些實施例中，該經摻雜之導電聚合物的分散液係捧合其他可溶或可分散於該氘化之液體介質的材料。該些添加劑係如上所述。 5·電子裝置可因具有包括本文中所述之氘化材料的一或多之層而受 145486.doc -37· 201127895 益的有機電子裝置’包括但不限於⑴將電能轉換成輻射能之裝置(例如’發光二極體、發光二極體顯示器、發光照明器具或二極體雷射）；⑺以電子方法偵測信號之裝置 (例如’光偵測器、光導電池、光敏電阻器、光控開關、光電晶體、光電管、紅外線偵測器）；（3)將輻射能轉換成電能之裝置（如’光伏打裝置或太陽能電池）；以及（4)包括一或多之電子組件的裝置（例如，電晶體或二極體），其中該(等)電子組件包括一或多之有機半導體層。本發明之化合物常可用之應用如氧氣敏感指示器及生物鑑定中的發光指示器（luminescent indicator)。在一實施例中，一有機電子裝置包含至少一層，該層包含（a)至少一氘化之導電聚合物以及（b)至少一高度氟化之酸聚合物。 a.第一示例性裝置一特別有用之電晶體種類，即薄膜電晶體（「TFT」），通常包括-間極、-在閘極上之閘介電質、—鄰接該閉介電貝之源極與汲極以及一鄰接該閘介電質與鄰接該源極與汲極的半導體層（請參見如S. M Sze，physkS QfSajiki, Fumiyo Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota 〇rS- Lett., 2004, 6 (9), 1485-1487 ° After deuteration of the conductive polymer, the HFAP and selective additives are as described above. Add it. In certain embodiments, the pH is raised before or after the addition of the selective additive. This pH can be adjusted by treatment with deuterated cation exchange resin and/or alkaline resin. In certain embodiments, the pH is adjusted by the addition of a D20 alkaline solution. The cation used in this test may be, but not limited to, alkali metal, alkaline earth metal, total cerium-ammonium and perylene-alkyl ammonium. In certain embodiments, the alkali metal is preferred to the alkaline earth metal cation. Films can be formed from the above compositions using any liquid deposition technique, including continuous or discontinuous techniques. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing. The film thus formed is continuous, smooth and relatively transparent. b. HFAP-doped deuterated conductive polymer. In certain embodiments, the HFAP-doped deuterated conductive polymer is formed by oxidative polymerization of the deuterated precursor monomer. The 145486.doc • 36- 201127895 HFAP (in a deuterated liquid medium) is carried out. In some embodiments, the consumable liquid medium is D2. The polymerization of the non-vaporized analog material is described in the published U.S. Patent Application Serial Nos. 2, 4, 4, 2, 577, 2004/0127, 637 and 2005/0205860. The resulting product is a liquid dispersion of a HFAp-doped sigma-based conductive polymer. In certain embodiments, the composition is selected from the group consisting of poly(D4-EDOT) and poly(D6_ED〇T) doped with a perfluorinated bismuth acid polymer, doped with a perfluorinated hydrazine acid. A group of poly(Ds-Py) and DyPam doped with a perfluorinated deuterated acid polymer. In certain embodiments, the perfluorinated vaporized acid polymer is a TFE (tetrafluoroethylene) and PSEPVE (perfluoro-3,6-dioxo-4-indolyl-7-octenesulfonic acid, The copolymer in which the acid proton has been exchanged for a ruthenium core. This material is abbreviated as "D_poly (TFE_pSEpvE)". Alternatively, a non-deuterated analog of the doped conductive polymer can be formed first, followed by deuteration of the material. In some embodiments, the partially settled material is treated to increase the degree of deuteration. The method of deuteration is a well-known technique, as described above. In some examples, the pH of the dispersion is increased as described above. The dispersion of the doped conductive polymer remains stable under the conditions of Qiu to neutral cation of about 2 at the time of formation. In certain embodiments, the dispersion of the doped conductive polymer holds other materials that are soluble or dispersible in the deuterated liquid medium. These additives are as described above. 5. An electronic device may be an organic electronic device that is beneficial to one or more layers including the deuterated material described herein, including but not limited to (1) a device that converts electrical energy into radiant energy. (eg 'light emitting diodes, light-emitting diode displays, illuminated lighting fixtures or diode lasers); (7) devices that detect signals electronically (eg 'photodetectors, photoconductive cells, photoresistors, light Control switch, photoelectric crystal, photocell, infrared detector); (3) devices that convert radiant energy into electrical energy (such as 'photovoltaic devices or solar cells); and (4) devices that include one or more electronic components ( For example, a transistor or a diode), wherein the (etc.) electronic component comprises one or more organic semiconductor layers. The compounds of the present invention are commonly used in applications such as oxygen sensitive indicators and luminescent indicators in bioassays. In one embodiment, an organic electronic device comprises at least one layer comprising (a) at least one deuterated electrically conductive polymer and (b) at least one highly fluorinated acid polymer. a. The first exemplary device is a particularly useful type of transistor, namely a thin film transistor ("TFT"), which typically includes a --electrode, a gate dielectric on the gate, and a source adjacent to the closed dielectric. a pole and a drain and a semiconductor layer adjacent to the gate dielectric and the source and drain (see, for example, S. M Sze, physkS Qf

Semiconductor Devices, 2"d edition, J〇hn Wiley and Sons, page 492)。這些組件可以各種組態加以裝配。一有機薄膜電晶體（0TFT)之特徵在於具有一有機半導體層。有機半導體層材料如恩（anthracence)、立體規則性聚噻吩 (regioregular polythiophenes)，皆為該項技術領域中所熟知者。該氘化之導電聚合物組成物若導電度大於ι〇 145486.doc -38- 201127895 S/cm，則在作為有機薄膜電晶體（「〇tft」）時特別有用。在一實施例中，一〇TpT包含：一基板一絕緣層；一閘極；一源極；一汲·極；以及一有機半導體層；其中至少-電極包含_氘化之導電聚合物，並且其中該絕緣層、為1極、該半導體層、該源極與錢極可以任何順序排列、，但前提是該閘極與該半導體層兩者皆接觸該絕緣層 °亥源極與該 >及極兩者皆ϋii： a α , S接觸S亥+導體層並且該些電極彼此並未互相接觸。在圖⑽示意說明_有機場效電晶體（0 =一裝置在「底部接觸模式」下活性層的相對位置= 二：:之「底部接觸模式」t，先將該没極與源極r“ 於该閘介電質層上後，再脾再將邊活性有機半導體層沉積於言源拽與汲極以及任何仍曝露之閘 44 && 層上。）一基板 11 係接觸於一閘極1 〇2與—絕绫 811 - ^ ^ ^ 、， s 04，該源極106與汲極10 則》儿積於該絕緣層1〇4頂部盆門Μ 士以上。覆盍於該源極與汲極上; ”間者為—有機半導體層110,其包含_式2化合物。圖ΙΒ為-OTFT之示意圖其顯示此模式下活性層的相對位置、頂接潑 1 (在頂部接觸楔戎，中，一 OTFT之汲極與源極係狀该活性有機半導體層之頂部 145486.doc •39· 201127895 上。) 圖1C為一 OTFT之示意圖，其顯示此一裝置在底部接觸模式下活性層的相對位置並且其閘極位於頂部。圖1D為一 0TFT之示意圖，其顯示此一裝置在頂部接觸模式下活性層的相對位置並且其閘極位於頂部。該基板可包含無機玻璃、陶瓷箔、聚合性材料（如丙烯酸聚合物、環氧樹脂、聚醯胺、聚碳酸酯、聚醯亞胺、聚酮、聚（氧基-1,4-伸苯氧基-1,4-伸苯羰基-1，4-伸苯基） (poly(oxy-1，4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) > 有時稱為聚（醚醚酮）或PEEK)、聚降莰烯 (polynorbornenes)、聚伸苯氧化物（polyphenyleneoxides)、聚（伸乙萘二叛酸 S旨）(P〇ly(ethylene naphthalenedicarboxylate, PEN)、聚（對苯二甲酸二乙酯）（PET)、聚（笨硫醚） (PPS))、填充聚合性材料（如纖維強化塑膠（FRP))與/或塗覆金屬箔。該基板之厚度可為約10微米至超過10毫米；例如對於一撓性塑膠基板而言，為約5 0至約10 0微米；並且對於一剛性基板如玻璃或石夕而吕’為約1至約1 〇宅米。通吊而言，一基板在製造、測試與/或使用期間會支樓該 OTFT。選擇性的是，該基板可知供'~~電功能如匯流排線連接至該源極、汲極以及該〇TFT的電極與電路。該閘極可為一薄金屬膜、一導電聚合物膜、一由導電墨水或糊膠所製成之導電膜或者該基板本身’例如使其換雜大量的矽。合適之閘極材料實例包括銘、金、鉻、姻錫氧化物、導電聚合物、包含碳黑或石墨之導電墨水/糊膠或 -40· 145486.doc 201127895 -在聚口物黏。劑中之膠體銀分散液。在某些〇TFT中，同材料可提供δ玄閘極功能並提供基板的支樓功能。例如’經捧雜之碎可作用為該閘極與支揮該0TFT。亥閘極可藉由下列製程製備，包括真空蒸鍍、金屬或導電金屬氧化物之濺鍍、使用旋轉塗布塗覆導電聚合物溶液或導電墨水、鑄造或印刷。對於金屬膜而t，該閘極之厚度可為如約10至約200奈米，對於聚合物導體而言，則為約1至約1 0微米。某一實她例中’该閘極包含一氘化之導電聚合物。名 ::實：：中’該閑極包含一氣化之導電聚合物，該以勺二雜：度氟化之酸聚合物。在某些實施例中，該閘招 ::⑷爪化之導電聚合物，該聚合物摻雜一非氟化之 =酸以及⑻-高度氣化之酸聚合物。在某些實施例中’ 導電叔子，《子係選自由金屬奈米粒子與奈米碳管所組成之群組。該源極與沒極可由對該半導體層提供—低電阻的材料所製成’所以該半導體層和該源極妾 Γ阻係低於該半導體層之電阻。通道電阻即為該半= 層之導電度。诵堂而導體作為源極與汲極之並型材料肖妊鈕、蛋阻適用材科包括鋁、鋇'鈣、鉻、金、 ’：、、、鈀、鉑、鈦與上述物質之合金；奈米碳管 4合物；在導電聚合物中之奈米 ’導電物中之金屬分散液;與上述物質…夜：在導電聚合適用於續半導體㈣些材料部分材科’而其他則適用於Ρ型半導體，此皆 I45486.doc -41 - 201127895 為熟悉該技術者所習知百斤各知。源極與汲極之典型厚度奈米至約1微米。在苹此力40 仕系些貫轭例中，該厚度為約1〇〇 400奈米。主、、勺在某些實施例中，# .E “ Α μ °玄源極與/或汲極包含一氘化之導雷聚合物。在某此音^ 电 -貫施例中，該源極與/或汲極包含一之導電聚口物’該聚合物摻雜一高度氣化之酸聚合物。在某些實施例中，該源極與/或没極包含⑷一氛化之導電聚口物》亥聚口物摻雜_非敗化之聚合性酸以及⑻—高度氟化之S文聚σ物。在某些實施例中’該電極進一步包含導電粒子’該粒子係選自由金屬奈米粒子與奈米碳管所組成之群組。該絕緣層包含—無機材料膜或—有機聚合物膜。適合作為絕緣層之無機材料的說明性實例包括氧化鋁、氧化石夕、氧化钽、氧化鈦、氮化矽、鈦酸鋇、鈦酸鋇锶、锆鈦酸鋇 (bamim Zlrconate titanate)、硒化鋅與硫化鋅。此外，前述材料之合金、組合與多層物皆可用於該絕緣層。用於該絕緣層之有機聚合物的說明性實例包括聚酯、聚碳酸酯、聚 (乙烯基酚）、聚醯亞胺、聚苯乙烯、聚（甲基丙烯酸）、聚 (丙烯酸酯）、環氧樹脂與上述物質之摻合物與多層物。該絕緣層之厚度為如約1〇奈米至約5〇〇奈米，取決於所使用 "電材料之介電常數。例如，該絕緣層之厚度可為約1 〇〇奈米至約500奈米。該絕緣層之導電度可為如低於約1〇·1：ί S/cm (其中S =西門子= 1/ohm)。 3亥絕緣層、該閘極、該半導體層、該源極與該沒極可以 145486.doc -42- 201127895 任何順序形成’只要該閘極與該半導體層兩者皆接觸該絕 :層並且該源極與該汲極兩者皆接觸該半導體層。片語以任何順序」包括依序形成與同時形成。例如，該源極 ” 5、極可依序形成或同時形成。可使用習知方法提供該閘極、該源極與該及極，如物理氣相沉積（例如，熱蒸链或滅鍍）或喷墨印刷。該些電極的圖案化可藉由習知方法而達成，例如陰影遮罩&、相加性光㈣法（additwe photolithography)、相減性光蝕刻法（_匕_ — photolithography)、印刷、微接觸印刷與圖案塗布。對於底部接觸模式之〇TFT(見圖1A)而言，分別形成用於源極與汲極之線路的電極1〇6與1〇8可使用一光蝕刻程序而創造於該二氧化矽層上。一半導體層11〇而後沉積於電極106與108及層1〇4之表面上。在某些實施例中，半導體層11〇包含一種或以上之有機半導體化合物。有機半導體通常基於··線性稠苯化合物 (acenes) ’例如稠四苯、稠五苯及其衍生物；噻吩，例如立體規則性养嗟吩（regi〇regUhr oligothiophenes)與立體規則性聚°塞吩；稠環噻吩-芳族與噻吩·伸乙烯基/伸芳基 (thiophene-vinylene/arylene)衍生物。該半導體層110可藉由各種該項技術領域中所習知的技術沉積。這些技術包括熱蒸鍍、化學氣相沉積、熱轉移、噴墨印刷與網版印刷。用於沉積之分散薄膜塗布技術包括方疋轉塗布、刮刀塗布、墜落式鑄造（dr0p casting)與其他習知技術。 H5486.doc -43- 201127895 對於頂部接觸模式之0Ti?T(見圖1B)而言，先將層no沉積於層104上後再製造電極106與108。 b ·第一不例性裝置本發明亦涉及-電子裝置，其包含至少-位於兩電接觸層間之電活性層中該裝置之至少一電活性層包含一氘化之導電t合物。在某些實施例中，該電活性層包含一氛化之導電聚合物’該聚合物摻雜一高度氟化之酸聚合物。在某些實施例中’該電活性層包含⑷一氘化之導電聚合物’该聚合物摻雜—非說化之聚合性酸以及⑻—高度氣化之馱聚合物。在某些實施例中，該電極進一步包含導電粒子，該粒子係選自由金屬奈米粒子與奈米碳管所組成之群組0 一有機電子裝置結構之另一實例係示於圖2。該裝置2〇〇具有一第一電接觸層、一陽極層210及一第二電接觸層、一陰極層260及在層間的一電活性層24〇。鄰接該陽極者可為一電洞注入層220。鄰接該電洞注入層者可為一電洞傳輸層230，其包含電洞傳輸材料。鄰接該陰極者可為一電子傳輸層250，其包含一電子傳輸材料。裝置可使用—戋多之緊鄰該陽極210的額外電洞注入或電洞傳輸層（圖未示）與/或一或多之緊鄰該陰極260之額外電子注入或電子傳輸層（圖未示）。層220至250個別地及統稱為活性層。在某些實施例中，該電活性層24〇為經像素化 (pixellated) ’如圖3所示。層240區分為像素或次像素單元 145486.doc •44- 201127895 241、242與243，其在該層上不斷重複，各像素或次像素單元代表一不同之顏色。在某些實施例中 '，該次像素單元為代表紅色、綠色與藍色。雖然圖中所示為三個次像素單元’但亦可使用兩個或超過三個。取決於該裝置200的應用，該電活性層240可為一由外加電壓啟動的發光層（例如在一發光二極體中或發光電化電池中），或為一在具有或不具有一外加偏壓下響應輻射能量並產生一信號之材料層（例如在一光偵測器中）。光偵測器之實例包括光導電池、光敏電阻、光控開關、光電晶體、光電管及光伏打電池，這些術語如同於J〇hn Markus 所著之「Electronics and Nucleonics Dictionary」中第 470 頁及第476頁（McGraw-Hill, Inc.出版，1966年）中所描述者。具有發光層之裝置可用以形成顯示器或用於照明應用’例如白光照明裝置。在某些貝施例中，該電洞注入層220包含一氛化之導電聚合物。在某些實施例中，該電洞注入層220包含（a)至少一氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸乂及（b)至少一向度氟化之酸聚合物。在某些實施例中，該電洞注入層220主要由（a)至少一氘化之導電聚合物，該聚合物摻雜一非氟化之聚合性酸以及（b)至少一高度氟化之酸聚合物所構成。在某些實施例中’該電洞注入層22〇包含至乂 —氘化之導電聚合物’該聚合物摻雜至少一高度氟化之酸聚合物。在某些實施例中，該電洞注入層22〇主要由至沙一氘化之導電聚合物所構成，該聚合物摻雜至少一高 145486.doc 45· 201127895 度氟化之酸聚合物。 ^裝置之其他層在考慮其所欲發揮之功能下，可用任何已知可用於此類層之材料製成。該裝置可包括-切件或基板（圖未㈤，該支板可鄰接於該陽極層21G或該陰極層勝最常見的是^ 支標件係、鄰接於該陽極m該支撐件可為換性或剛性、有機或無機。切件材料的實例包括但不限於玻璃、陶瓷、金屬及塑膠獏。相較於該陰極層260,該陽極層21〇為一對於注入電洞較有效率之電極。因此，該陽極具有較該陰極為高之功函數。該陽極可包括含有一金屬、混合金屬、合金、金屬氧化物或混合氧化物之材料。合適的材料包括第2族元素（即 Be、Mg、Ca、Sr、Ba、Ra)之混合氧化物、第⑴矣元素、第4、5與6族中的元素及第8·1()族的過渡元素。若該陽極層210需具有光穿透性，則可使用第12、13與14族之元素。如本文中所用f ’片語「混合氧化物」係指具有兩種或以上之不同陽離子的氧化物，該陽離子係選自第2族元素或第12、13或14族元素。合適材料之實例包括但不限於銦錫氧化物（「ITO」）、銦辞氧化物（Γ IZ〇」）、鋁錫氧化錄錫氧化物Semiconductor Devices, 2"d edition, J〇hn Wiley and Sons, page 492). These components can be assembled in a variety of configurations. An organic thin film transistor (0TFT) is characterized by having an organic semiconductor layer. Organic semiconductor materials such as anthracence and regioregular polythiophenes are well known in the art. The conductive conductive polymer composition is particularly useful as an organic thin film transistor ("〇tft") if its conductivity is greater than ι 145486.doc -38 - 201127895 S/cm. In one embodiment, a TpT comprises: a substrate-insulating layer; a gate; a source; a germanium electrode; and an organic semiconductor layer; wherein at least the electrode comprises a germanium-based conductive polymer, and Wherein the insulating layer is a pole, the semiconductor layer, the source and the money pole may be arranged in any order, provided that both the gate and the semiconductor layer contact the insulating layer and the source> And both are ϋii: a α , S contacts the S + + conductor layer and the electrodes do not contact each other. Figure (10) shows schematically _ there is an airport effect transistor (0 = relative position of the active layer in a "bottom contact mode" = 2:: "bottom contact mode" t, first the source and source r" After the gate dielectric layer, the spleen deposits the edge active organic semiconductor layer on the source and drain electrodes and any remaining exposed gates 44 &&<> The poles 1 〇 2 and 绫 811 - ^ ^ ^ , s 04, the source 106 and the drain 10 are accumulated above the top of the insulating layer 1 〇 4 。。。。。。。。。。。。。 And the bungee; "intermediate" is an organic semiconductor layer 110 comprising a compound of formula 2. Figure ΙΒ is a schematic diagram of -OTFT which shows the relative position of the active layer in this mode, topping splash 1 (in the top contact wedge, in the top of an OTFT and the source is the top of the active organic semiconductor layer 145486. Doc •39· 201127895.) Figure 1C is a schematic diagram of an OTFT showing the relative position of the active layer in the bottom contact mode of this device and its gate at the top. Figure 1D is a schematic illustration of a 0TFT showing the relative position of the active layer in the top contact mode of the device and its gate at the top. The substrate may comprise inorganic glass, ceramic foil, polymerizable material (such as acrylic polymer, epoxy resin, polyamine, polycarbonate, polyimide, polyketone, poly(oxy-1,4-benzene) Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) > sometimes called poly( Ether ether ketone) or PEEK), polynorbornenes, polyphenylene oxides, poly(ethylene naphthalenedicarboxylate, PEN), poly(pair) Diethyl phthalate) (PET), poly(phenylene sulfide) (PPS), filled with polymeric materials (such as fiber reinforced plastic (FRP)) and/or coated metal foil. The thickness of the substrate can be about 10 microns to over 10 mm; for example, from about 50 to about 10 microns for a flexible plastic substrate; and from about 1 to about 1 for a rigid substrate such as glass or stone. In the case of hanging, a substrate will support the OTFT during manufacture, testing, and/or use. Alternatively, the substrate can be used for '~~ electrical functions such as bus lines. Connecting to the source, the drain, and the electrode and the circuit of the TFT. The gate can be a thin metal film, a conductive polymer film, a conductive film made of conductive ink or paste, or the substrate itself. 'For example, to make a lot of defects. Suitable examples of gate materials include Ming, gold, chromium, tin oxide, conductive polymers, conductive inks containing carbon black or graphite / paste or -40·145486.doc 201127895 - Colloidal silver dispersion in poly-stick adhesive. In some 〇TFT, the same material can provide δ 玄 gate function and provide the function of the branch of the substrate. For example, The gate and the TFT are supported. The gate can be prepared by the following processes, including vacuum evaporation, sputtering of metal or conductive metal oxide, coating of conductive polymer solution or conductive ink using spin coating, casting or printing For a metal film and t, the thickness of the gate may be, for example, about 10 to about 200 nanometers, and for a polymer conductor, about 1 to about 10 micrometers. Contains a conductive polymer. Name:: Real:: Medium' The idler comprises a gasified conductive polymer, which is a scavenger: fluorinated acid polymer. In some embodiments, the gate is: (4) a clawed conductive polymer, the polymer is doped with a polymer Non-fluorinated=acid and (8)-highly vaporized acid polymer. In some embodiments, 'conductive uncle, the sub-system is selected from the group consisting of metal nanoparticles and carbon nanotubes. The source The semiconductor layer and the source resistance are lower than the resistance of the semiconductor layer. The channel resistance is the conductivity of the half = layer.诵而而导体导体而而而而导体导体导体导体导体导体导体导体妊妊妊妊妊妊妊妊妊妊、、、、、、、、、、、、、、、、、、、、、、、、 a carbon nanotube 4 compound; a metal dispersion in a nano conductor in a conductive polymer; and the above substances... night: in conductive polymerization suitable for continuing semiconductors (4) some materials part of the material' while others apply to Ρ-type semiconductors, all of which are known to those skilled in the art, I45486.doc -41 - 201127895. The typical thickness of the source and the bungee is from about 1 micron. In the case of the yoke, the thickness is about 1 〇〇 400 nm. In some embodiments, the #.E" Α μ ° source and/or the drain contains a deuterated guide polymer. In some of the sounds, the source The pole and/or the drain comprises a conductive agglomerate 'the polymer is doped with a highly vaporized acid polymer. In some embodiments, the source and/or the poleless comprises (4) a condensed conductive Agglomerate _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A group consisting of a metal nanoparticle and a carbon nanotube. The insulating layer comprises an inorganic material film or an organic polymer film. Illustrative examples of inorganic materials suitable as an insulating layer include alumina, oxidized oxide, oxidation Bismuth, titanium oxide, tantalum nitride, barium titanate, barium titanate, babim Zlrconate titanate, zinc selenide and zinc sulfide. In addition, alloys, combinations and multilayers of the foregoing materials can be used for the Insulating layer. Illustrative examples of organic polymers used in the insulating layer include polyester, poly a blend of an acid ester, a poly(vinylphenol), a polyimide, a polystyrene, a poly(methacrylic acid), a poly(acrylate), an epoxy resin, and a plurality of layers. The thickness is, for example, from about 1 nanometer to about 5 nanometers, depending on the dielectric constant of the electrical material used. For example, the thickness of the insulating layer may range from about 1 nanometer to about 500 nanometers. The insulating layer may have a conductivity of, for example, less than about 1 〇·1: ί S/cm (where S = Siemens = 1/ohm). 3 ing insulating layer, the gate, the semiconductor layer, the source and the Nothing can be formed 145486.doc -42- 201127895 in any order as long as the gate and the semiconductor layer are in contact with the layer: and the source and the drain are both in contact with the semiconductor layer. The sequence includes sequential formation and simultaneous formation. For example, the source "5" may be formed sequentially or simultaneously. The gate, the source and the pole may be provided using conventional methods, such as physical vapor deposition (eg, hot steaming or de-plating) Or inkjet printing. The patterning of the electrodes can be achieved by conventional methods, such as shadow mask & additwe photolithography, subtractive photolithography (_匕__ photolithography) ), printing, micro-contact printing and pattern coating. For the bottom contact mode 〇 TFT (see Fig. 1A), the electrodes 1〇6 and 1〇8 respectively forming the lines for the source and the drain can use a light. An etch process is created on the ruthenium dioxide layer. A semiconductor layer 11 is then deposited on the surfaces of the electrodes 106 and 108 and the layers 1-4. In some embodiments, the semiconductor layer 11 〇 contains one or more organic layers. Semiconductor compounds. Organic semiconductors are usually based on linear benzene compounds (acenes) such as fused tetraphenyl, fused pentabenzene and derivatives thereof; thiophenes such as regi〇regUhr oligothiophenes and stereoregular poly ° Cyclophene-aromatic and thiophene-vinylene/arylene derivatives. The semiconductor layer 110 can be deposited by various techniques known in the art. These techniques include thermal steaming. Plating, chemical vapor deposition, thermal transfer, inkjet printing and screen printing. Dispersion film coating techniques for deposition include square-turn coating, knife coating, drop casting (dr0p casting) and other conventional techniques. Doc -43- 201127895 For the top contact mode 0Ti?T (see Fig. 1B), the electrodes no are deposited on the layer 104 before the electrodes 106 and 108 are fabricated. b. The first exemplary device also relates to An electronic device comprising at least one electroactive layer between the two electrical contact layers, the at least one electroactive layer of the device comprising a deuterated conductive t-compound. In some embodiments, the electroactive layer comprises an atmosphere Conductive polymer 'The polymer is doped with a highly fluorinated acid polymer. In some embodiments 'the electroactive layer comprises (4) a deuterated conductive polymer 'the polymer is doped - non-speech Polymeric acid and (8) - height In some embodiments, the electrode further comprises conductive particles selected from the group consisting of metal nanoparticles and carbon nanotubes. Another example structure of an organic electronic device structure 2, the device 2 has a first electrical contact layer, an anode layer 210 and a second electrical contact layer, a cathode layer 260 and an electroactive layer 24 层 between the layers. A layer 220 is implanted into a hole. Adjacent to the hole injection layer may be a hole transport layer 230 comprising a hole transport material. Adjacent to the cathode can be an electron transport layer 250 comprising an electron transport material. The device may use an additional hole injection or hole transport layer (not shown) adjacent to the anode 210 and/or one or more additional electron injection or electron transport layers adjacent to the cathode 260 (not shown). . Layers 220 through 250 are individually and collectively referred to as active layers. In some embodiments, the electroactive layer 24 is pixelated as shown in FIG. Layer 240 is divided into pixel or sub-pixel units 145486.doc • 44- 201127895 241, 242, and 243, which are repeated on this layer, with each pixel or sub-pixel unit representing a different color. In some embodiments, the sub-pixel unit is representative of red, green, and blue. Although three sub-pixel units are shown in the figure, two or more than three may be used. Depending on the application of the device 200, the electroactive layer 240 can be an emissive layer that is activated by an applied voltage (eg, in a light emitting diode or in a light-emitting electrochemical cell), or one with or without an external bias. A layer of material that responds to the radiant energy and produces a signal (eg, in a photodetector). Examples of photodetectors include photoconductive cells, photoresistors, photoswitches, optoelectronic crystals, photocells, and photovoltaic cells. These terms are as described in J.hn Markus's "Electronics and Nucleonics Dictionary" on pages 470 and 476. As described in the page (published by McGraw-Hill, Inc., 1966). A device having a light-emitting layer can be used to form a display or for a lighting application, such as a white light illumination device. In some embodiments, the hole injection layer 220 comprises an encapsulated conductive polymer. In some embodiments, the hole injection layer 220 comprises (a) at least one deuterated conductive polymer doped with a non-fluorinated polymeric acid bismuth and (b) at least one-dimensional fluorinated Acid polymer. In some embodiments, the hole injection layer 220 is mainly composed of (a) at least one deuterated conductive polymer doped with a non-fluorinated polymeric acid and (b) at least one highly fluorinated Made up of acid polymers. In some embodiments, the hole injection layer 22 includes a conductive polymer that is doped to the germanium. The polymer is doped with at least one highly fluorinated acid polymer. In some embodiments, the hole injection layer 22 is composed primarily of a conductive polymer that is fused to a sand, and the polymer is doped with at least one fluorinated acid polymer of 145486.doc 45·201127895 degrees. ^ Other layers of the device may be made of any material known to be useful for such layers, taking into account the function desired. The device may comprise a cutting member or a substrate (Fig. 5 (five), the supporting plate may be adjacent to the anode layer 21G or the cathode layer is most common to be a standard member system, adjacent to the anode m, the support member may be replaced Sexual or rigid, organic or inorganic. Examples of cutting material include, but are not limited to, glass, ceramic, metal, and plastic enamel. Compared to the cathode layer 260, the anode layer 21 is an electrode that is more efficient for injecting holes. Thus, the anode has a higher work function than the cathode. The anode may comprise a material comprising a metal, a mixed metal, an alloy, a metal oxide or a mixed oxide. Suitable materials include Group 2 elements (ie, Be, a mixed oxide of Mg, Ca, Sr, Ba, Ra), a (1)th germanium element, an element of groups 4, 5 and 6 and a transition element of group 8.1(). If the anode layer 210 is required to have light For penetrability, elements of Groups 12, 13 and 14 can be used. As used herein, the term 'mixed oxide' refers to an oxide having two or more different cations selected from the group consisting of Group 2 elements or Group 12, 13 or 14 elements. Examples of suitable materials But not limited to indium tin oxide ("ITO"), indium oxide (ΓIZ〇), aluminum tin oxide tin oxide

物（「ΑΤΟ」）、鋁鋅氧化物（「AZO (「ΖΤΟ」）、金、銀、銅與鎳。在某些實施例中’該混合氧化物層係經圖案化。該圖案可根據需求改變。該層可藉由如使用一非連續沉積技術來形成一圖案。或者，該層可施用為一整體層（亦稱為毯式 145486.doc • 46 * 201127895 沉積隨後使用如-圖案化光阻層及濕式化學或乾式钱刻技術來加以圖案化。亦可❹該項技術領域所熟知的其它圖案化程序。、在某些實施例中，ϋ擇性之電洞傳輸層23〇係存在於電洞注入層220與電活性層240間。用於該電洞傳輸層之電洞傳輸材料已歸納如於Y. Wang之Kirk_〇thmer化工百科全書 (Kirk-Othmer Encyclopedia of Chemical Technology) , f 4 版’第18卷，第837至860頁（1996年）之中。可使用電洞傳輸小分子及聚合物兩者。一般使用的電洞傳輸分子包括但不限於：4,4'，4"-參（N，N-聯苯-胺基）_三苯胺（TDATA); 4,4'，4"-參（N-3-曱基笨基苯基-胺基）_三苯胺 (MTDATA) ; N，N’-二苯-N，N，-雙（3-甲基苯基[[u-聯苯]_ 4,4'-二胺（TPD); 4，4'-雙（咔唑-9-基）聯苯（CBP); 1，3-雙（咔嗤_9_基）苯（mCP) ·’ 1，1-雙[(di-4-曱苯基胺基）苯基]環己烷 (TAPC) ; N，N’-雙（4-甲基苯基）-N，N'-雙（4-乙基苯基）-[ι，ι，_ (3,3L二曱基）聯苯]-4,4’-二胺（ETPD);肆-(3-甲基苯基）-队：^，：1^，>1|-2,5-伸苯二胺（？〇八）；01-苯基-4-^[，^[-聯苯胺基苯乙烯（TPS);對-(二乙基胺基）苯甲醛聯苯腙（DEH);三笨胺 (TPA);雙[4-(N,N-二乙基胺基）-2-甲基苯基](4-曱基苯基）曱烷（MPMP) ; 1-苯基-3-[對-(二乙基胺基）苯乙烯基]-5-[對-(二乙基胺基）苯基]吼唑啉（PPR或DEASP) ; 1,2-反-雙 (9H-咔唑-9-基）環丁烷（DCZB) ; N，N，N’，N'-肆（4-甲基苯基）-(1，厂-聯苯）-4,4'-二胺（TTB) ; N，N’-雙（萘-1-基）-Ν,Ν’-雙-(苯基）聯苯胺（α-ΝΡΒ);以及紫質化合物如銅酞青。一般使用 145486.doc • 47- 201127895 的電洞傳輸聚合物包括但不限於聚乙烯咔唑 (polyvinylcarbazole)、（苯基甲）聚石夕烧（(phenyimethyl)p〇lySiiane)、聚（二氧°塞吩）(P〇1y(dioxythiophenes))、聚苯胺（p〇lyaniiines) 以及聚°比咯（polypyrroles)。藉由將像上述那些的電洞傳輸分子摻雜至像聚苯乙烯及聚碳酸醋之聚合物中，亦可能獲得電洞傳輸聚合物。在某些情況中，使用三芳胺聚合物，尤其是使用三芳胺-苐共聚合物。在某些情況中，該等聚合物及該等共聚合物係可交聯的。可交聯電洞之傳輸聚合物的可發現於如已公開之美國專利申請案第2〇〇5_〇184287 號及已公開之PCT申請案第WO 20〇5/〇52〇27號。在某些實施例中，該電洞傳輸層摻雜一 p型摻雜劑（p_d〇pant)，例如四氣四氰嗜二曱烧（tetrafluorotetracyanoquinodimethane)和茈-3,4,9，10-四羧-3,4,9，10-土酐。取決於該裝置的應用’該電活性層240可為一由一外加電壓啟動之發光層（例如在一發光二極體中或發光電化電池中）’ 一在具有或不具有一外加偏壓下響應輕射能量並產生一信號之材料層（例如在一光偵測器中）。在一實施例中’該電活性材料為一有機電致發光（「EL」）材料。任何有機電致發光材料皆可使用在該些裝置中，包括但不限於小型分子有機螢光化合物、螢光與磷光金屬錯合物、共輕聚合物與上述物質之混合物。螢光化合物之實例包括但不侷限於薇（chrysenes)、祐（pyrenes)、花（perylenes)、紅蟹細（rubrenes)、香豆素（coumarins)、蒽（anthracenes)、嗟二唾（thiadiazoles)、上述物質之衍生物及上述物質之混合 I45486.doc -48 - 201127895 物。金屬錯合物之實例包括但不限於金屬螯合咢辛類 (oxinoid)化合物，如參（8-羥基喹啉配位基）鋁（Alq3);環金屬化（cyclometalated)銥與翻電致發光化合物’例如Petrov et al.之美國專利第6,670,645號和公開之PCT申請案第W〇 03/063 555及WO 2004/016710號所揭露之銥與苯吡啶、苯喹啉或苯嘧啶配位基的錯合物，以及例如在公開之PCT申請案第 WO 03/008424、WO 03/091688 及 WO 03/040257 號所述之有機金屬錯合物以及上述物質之混合物。在某些情況中，該小分子螢光或有機金屬材料係沉積作為主材料中之摻雜劑，以改良加工與/或電子特性。共軛聚合物之實例包括但不限於聚（苯伸乙稀）(卩〇1丫(卩1^11}^16116¥丨117161^5))、聚苐（polyfluorenes)、聚（螺聯苐）(poly(spirobifluorenes))、聚0塞吩（polythiophenes)、聚（對伸苯）(poly(p-phenylenes))、上述物質之共聚物及上述物質之混合物。選擇性之電子傳輸層250可為有利於電子注入/傳輸兩種功能，並且亦可作為一圍阻層以避免層界面間之淬滅反應。更特定言之，層250可促進電子移動率與降低淬滅反應之可能性，否則層240與260會直接接觸。可用於該選擇性層250之電子傳輸材料實例括但不限於金屬螫合咢辛類 (oxinoid)化合物，其包括金屬喹啉衍生物如參（8-羥基喹啉配位基呂（tris(8-hydroxyquinolato)aluminum, A1Q)、雙（2-曱基-8-羥基喹啉配位基）（對-苯基氧苯基）鋁（bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum, BAlq)、肆-(8-羥基喹啉配位基）铪（HfQ)與肆-(8-羥基喹啉配位基）锆 145486.doc •49- 201127895 (ZrQ);以及唑化合物如2- (4-聯苯基基）-5-(4-三級丁基苯基）-1’3’4-呤二唑（PBD)、3_(4_聯苯基基）_4_苯基_5_(4_三級丁基苯基）-1，2,4-***（TAZ)與1，3,5·三（苯基·2-苯并咪唑）苯 (ΤΡΒΙ);喹唠啉（quin〇xaline)衍生物如2,3_雙㈠氟苯基）喹 "可啉，啡啉如4,7-二苯基-ΐ，ι〇_啡啉（DPA)與2,9_二甲基_ 4,7-二苯基_u〇_啡啉（DDpA);以及上述物質的混合物。在某些實施例中，該電子傳輸層進一步包括一 η型摻雜劑。N型摻雜劑材料係為熟知技術。該n型摻雜劑包括但不限於第1及2族金屬，第1及2族金屬鹽，例如LiF、CsF與 Cs2C〇3，第1及2族金屬有機化合物，例如Li喹啉⑴ q_late);以及分子n型摻雜物，例如無色染料、金合物例如W2(hPP)4，其中咖=1，3,4,6,7,8_六氣_211“密〇定并曰· [l，2-a]-嘧啶與鈷莘、四噻稠四苯、雙（伸乙二硫）四噻富瓦烯、雜環自由基或雙自由基與雜環自由基或雙自由基之二聚物、寡聚物、聚合物、雙螺化合物與多環。陰極層260為對於注入電子或負電荷載體特別有效率電極。陰極層26〇可為具有較第—電接觸層（於本例中為極層2U))為低之,力函數的任何金屬或非金屬。該陰極2 為一對於注人電子或負電荷載體特別有效率的電極。該極可為任何具有較該陽極低之功函數的金屬或非金屬。於該陰極的材料可選自第1族驗金屬（如U、Cs)、第2族( 屬f 12知金屬，包括稀土元素及鋼系元素與納可使用例如紹、銦、_、鋇、彭和鎖以及其組合材料。亦可在該有機層及該陰極層間沉積含U有機金屬 145486.doc -50· 201127895 口物LiF、Li20、合Cs有機金屬化合物、CsF、CS2〇及("ΑΤΟ"), aluminum zinc oxide ("AZO ("ΖΤΟ"), gold, silver, copper and nickel. In some embodiments 'the mixed oxide layer is patterned. The pattern can be as needed The layer may be formed by, for example, using a discontinuous deposition technique. Alternatively, the layer may be applied as a monolithic layer (also known as blanket 145486.doc • 46 * 201127895 deposition followed by use of - patterned light The resist layer and wet chemical or dry engraving techniques are used for patterning. Other patterning procedures well known in the art can be used. In some embodiments, the selective hole transport layer 23 It exists between the hole injection layer 220 and the electroactive layer 240. The hole transport material for the hole transport layer has been summarized in the Kirk-Othmer Encyclopedia of Chemical Technology by Y. Wang. , f 4 Edition, vol. 18, pp. 837-860 (1996). Holes can be used to transport both small molecules and polymers. Commonly used hole transport molecules include, but are not limited to: 4, 4' ,4"-Fin (N,N-biphenyl-amino)-triphenylamine TDATA); 4,4',4"-Find (N-3-decylphenylphenyl-amino)-triphenylamine (MTDATA); N,N'-diphenyl-N,N,-bis (3 -methylphenyl[[u-biphenyl]-4,4'-diamine (TPD); 4,4'-bis(carbazol-9-yl)biphenyl (CBP); 1,3-double (咔嗤_9_yl)benzene (mCP) ·' 1,1-bis[(di-4-fluorenylphenyl)phenyl]cyclohexane (TAPC); N,N'-double (4-A Phenyl)-N,N'-bis(4-ethylphenyl)-[ι,ι,_(3,3L dimercapto)biphenyl]-4,4'-diamine (ETPD); -(3-methylphenyl)-team: ^,:1^,>1|-2,5-phenylenediamine (??); 01-phenyl-4-^[,^[- Benzidine styrene (TPS); p-(diethylamino)benzaldehyde biphenyl hydrazine (DEH); tris-amine (TPA); bis[4-(N,N-diethylamino)- 2-methylphenyl](4-mercaptophenyl)decane (MPMP); 1-phenyl-3-[p-(diethylamino)styryl]-5-[p--(two Ethylamino)phenyl]oxazoline (PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N' -肆(4-methylphenyl)-(1, plant-biphenyl)-4,4'-diamine (TTB); N,N'-bis(naphthalen-1-yl)-oxime, Ν'- Double-(benzene Benzobenzidine (α-ΝΡΒ); and a purple compound such as copper indigo. Generally used 145486.doc • 47- 201127895 hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenyl) poly(phenymethyl) p〇lySiiane, poly (diox) P〇1y (dioxythiophenes), polyaniline (p〇lyaniiines) and polypyrroles. It is also possible to obtain a hole transporting polymer by doping a hole transporting molecule such as those described above into a polymer such as polystyrene and polycarbonate. In some cases, triarylamine polymers are used, especially triarylamine-ruthenium copolymers. In some cases, the polymers and the copolymers are crosslinkable. The transportable polymer of the cross-linkable hole can be found in, for example, the published U.S. Patent Application Serial No. 2, No. 5, 184, 287, and the published PCT Application No. WO 20 〇 5/ 〇 52 〇 27. In some embodiments, the hole transport layer is doped with a p-type dopant (p_d〇pant), such as tetrafluorotetracyanoquinodimethane and 茈-3,4,9,10-four. Carboxylic-3,4,9,10-earth anhydride. Depending on the application of the device 'the electroactive layer 240 can be an illuminating layer activated by an applied voltage (for example in a light-emitting diode or in a luminescent battery) - with or without an applied bias A layer of material that responds to light energy and produces a signal (eg, in a photodetector). In one embodiment, the electroactive material is an organic electroluminescent ("EL") material. Any organic electroluminescent material can be used in such devices, including but not limited to small molecular organic fluorescent compounds, fluorescent and phosphorescent metal complexes, co-light polymers and mixtures thereof. Examples of fluorescent compounds include, but are not limited to, chrysenes, pyrenes, perylenes, rubrenes, coumarins, anthracenes, thiadiazoles. , a derivative of the above substances and a mixture of the above substances I45486.doc -48 - 201127895. Examples of metal complexes include, but are not limited to, metal chelating oxinoid compounds such as quinone (8-hydroxyquinoline ligand) aluminum (Alq3); cyclometalated ruthenium and electroluminescence Compounds such as those disclosed in U.S. Patent No. 6,670,645 to Petrov et al., and PCT Application Nos. WO 03/063 555 and WO 2004/016710, both of which are related to phenylpyridine, benzoquinoline or phenylpyrimidine ligands. The complexes, as well as the organometallic complexes described in the published PCT application Nos. WO 03/008424, WO 03/091688 and WO 03/040257, and mixtures of the above. In some cases, the small molecule fluorescent or organometallic material is deposited as a dopant in the host material to improve processing and/or electronic properties. Examples of conjugated polymers include, but are not limited to, poly(phenylene bromide) (卩〇1丫(卩1^11}^16116¥丨117161^5)), polyfluorenes, poly(spigot) (poly(spirobifluorenes)), polythiophenes, poly(p-phenylenes), a copolymer of the above, and a mixture of the above. The selective electron transport layer 250 can be both advantageous for electron injection/transportation and can also act as a barrier layer to avoid quenching reactions between layer interfaces. More specifically, layer 250 promotes electron mobility and reduces the likelihood of quenching reactions that would otherwise be in direct contact with layers 240 and 260. Examples of electron transporting materials that can be used in the selective layer 250 include, but are not limited to, metal oxinoid compounds including metal quinoline derivatives such as quinone (8-hydroxyquinoline ligand lysine (tris) -hydroxyquinolato)aluminum, A1Q), bis(2-methyl-8-quinolinolato) (p-phenylphenolato) Aluminum, BAlq), 肆-(8-hydroxyquinoline ligand) ruthenium (HfQ) and ruthenium-(8-hydroxyquinoline ligand) zirconium 145486.doc •49- 201127895 (ZrQ); and azole compounds such as 2-(4-biphenylyl)-5-(4-tri-butylphenyl)-1'3'4-oxadiazole (PBD), 3-(4-diphenyl)-4_phenyl _5_(4_Tributylphenyl)-1,2,4-triazole (TAZ) and 1,3,5·tris(phenyl-2-benzoimidazole)benzene (hydrazine); quinoxaline (quin〇xaline) derivatives such as 2,3_bis(mono)fluorophenyl)quino"porphyrin, morpholine such as 4,7-diphenyl-indole, ι〇_phenoline (DPA) and 2,9_ Dimethyl-4,7-diphenyl-u〇-morpholine (DDpA); and mixtures of the above. In some embodiments, the electron transport layer further comprises an n-type dopant. N-type dopant materials are well known techniques. The n-type dopant includes, but is not limited to, Group 1 and 2 metals, Group 1 and 2 metal salts such as LiF, CsF and Cs2C〇3, Group 1 and 2 organometallic compounds such as Li quinoline (1) q_late) And molecular n-type dopants, such as leuco dyes, gold compounds such as W2 (hPP) 4, where coffee = 1,3,4,6,7,8_six gas _211" 密〇定曰 [ [ 1,2-a]-pyrimidine with cobalt ruthenium, tetrathia condensed tetraphenyl, bis(ethylenedithio)tetrathiafulvalene, heterocyclic radical or diradical and heterocyclic radical or diradical a polymer, an oligomer, a polymer, a spiro compound, and a polycyclic ring. The cathode layer 260 is a particularly efficient electrode for injecting electrons or a negative charge carrier. The cathode layer 26 can have a relatively first electrical contact layer (in this example) The middle layer is 2U)) is any metal or non-metal that is a low force function. The cathode 2 is an electrode that is particularly efficient for injection of electrons or negative charge carriers. The pole can be any lower than the anode. The metal or non-metal of the work function. The material of the cathode may be selected from the group 1 metal (such as U, Cs), the second group (genus f 12 metals, including rare earth elements and steel elements) Nano can use, for example, Shao, Indium, _, 钡, Peng and lock, and combinations thereof. It is also possible to deposit U-containing organic metal between the organic layer and the cathode layer. 145486.doc -50· 201127895 Oral LiF, Li20, and Cs organometallic Compound, CsF, CS2 and

Cs2C〇3以降低操作電壓。此層可稱為—電子注人層。只陰極層26G通吊藉由—化學或物理氣相沉積程序來形成。在某些實施例中，該陰極層係經圖案化，請參照上述之这極層21 〇。在某些實施例中示）’以防止不欲之，在該接觸層260上沉積一封裝層（圖未成分如水及氧進入裝置2〇〇中。此等成分對該有機層240可造成封裝層係一障壁層或膜。璃蓋。一有害效應。在一實施例中，該在一實施例中，該封裝層係一玻雖然圖未示，應理解該裝置2〇〇可包括額外層。可使用該項技術領域中已知或未知的其它層。此外，任何上述該等層可包括兩個或以上之次層(sub — layer)，或可形成一層狀結構。或者，可對陽極層21 〇、該電洞注入層22〇、該電洞傳輸層230、該電子傳輸層25〇、陰極層26〇及其它層之部分或全部進行處理，尤其是進行表面處理，以增加該裝置的電街載體傳輸效率或其它物理性質。對於每一成分層而言，所選擇的材料較佳係藉由下列方式而決定，即在考量裝置操作性壽命、製造時間與複雜度因素以及熟悉該技術者所知的其它考慮因素下，仍使提供一具有高裝置性能之裝置的目標達到平衡。應理解，對於該項技術領域具有通常知識者而言，決定最佳成分、成分組態及組成識別乃是常規技術。在一實施例中’該些不同層具有下述厚度範圍：陽極 145486.doc •51 · 201127895 210，500-5000 A，在一實施例中為1000-2000 A ;電洞注入層220 ’ 50-3 000 A，在一實施例中為200_ 1000 A ;選擇性之電洞傳輸層230，5〇-2〇00 A，在一實施例中為200- 1000 A ;電活性層240，10-2000 A，在一實施例中為200- 1000 A ;選擇性之電子傳輸層250，50-2000 A，在一實施例中為200-1000 A ;陰極260，200-10000 A，在一實施例中為300-5000 A。各層之相對厚度可影響該電子-電洞復合區在該裝置中之位置，並且因而影響該裝置之發射光譜。因此，應選擇該電子傳輸層之厚度以使該電子電洞複合區位於該發光層中。所欲之層厚度比例將取決於所用之材料的4切性質。在操作中，一來自一適當電力供應（圖未示）的電壓會施加於該裝置200。電流因此橫越通過該裝置2〇〇之該些層。電子進入該有機聚合物層，釋出質子。在某些〇led中，即所谓的主動矩陣OLED顯示器，電活性有機膜的個別沉積可猎纟t流通過而激發，致使個別像素的光發射。在某 4_OLED中，即所謂的被動矩陣见肋顯示器，電活性有機膜的/冗積可藉由電接觸層之行與列而激發。儘S類似或等效於此處所說明之方法及材料可用於實踐 ^測試本發明，但適當之方法及材料描述如下。本文中所 ^及之所有公開案、專利巾請案、專利及其他參考文獻以用的方式全部併入本文中。在發生衝突的情況下，以包 =義在内之本說明書為準。此外，料材料、方法例僅係說明性暂，；^ τ立，月Γ生負而不意欲為限制拘束。 145486.doc •52- 201127895 實例實例1 此實例說明氘化一 HFAP以形成一氘化HFAP。其進一步說明在二氧化氘（〇2〇)中之氘化HFAP分散液的製備。將四氟乙烯（「TFE」）與全氟-3,6-二氧-4-曱基_7-辛烯磺酸（「PSEPVE」）之共聚合物氣化，並以下列方式製成為一在〇2〇中之膠體分散液。首先將在磺酸中每987克（每—酸性位點該共聚物之重量）具有一質子的聚（TFE psEpvE)製成水分散液’其使用之製程類似於美國專利第6，15〇,426號之實例1，第2部分的製程，除了其溫度為約27〇<)(：。將該非氘化之聚（TFE-PSEPVE)分散液在一托盤上轉化為聚 (TFE-PSEPVE)之自由流動固體薄片，該托盤之液體深度不大於5/8’’。而後先將該托盤冷卻至低於(TC以冷凍該水分散液。一經冷凍，使其經過一不高於1 mm Hg之部分真二/C力直到移除大部分水分。而後將該部分乾燥固體在真工壓力下加熱至約3 〇 c ，以完全去除濕氣而不聚結 (coalescing)該聚合物。將21 g之非氘化聚（TFE-pSEPVE)固體薄片（已在真空烘粕中預乾燥以去除水分）置於以氮氣預吹洗之金屬圓柱管中。將購自 Cambridge lS0t0pe Lab，―之 15〇 g 〇2〇立即加入裝有該聚（TFE-PSEPVE)之管中。將該管加蓋，並於一壓力實驗室中加熱至約27〇t持續一段短時間後冷卻至室以確保6亥固體薄片轉化為在D2〇中之聚（TFE-PSEPVE) 勝體刀政液。此外，在極度過量之氘中的聚（TFE_ 145486.doc •53. 201127895 PSEPVE)當中之質子係已與氘進行交換，而完成聚（TFE-PSEPVE)之說化。將該在D20中的沉化聚（TFE-PSEPVE) (「D-聚（TFE-PSEPVE)」）分散液進一步處理以移除較大之粒子。該D-聚（TFE-PSEPVE)在該D20分散液中之重量％經測重法測定為11.34 wt.%，此比例係基於該分散液之總重量。實例2 此實例說明形成一氘化HFAP與一在二氧化氘（D20)中之氘化HFAP分散液的直接方法。可將四氟乙烯（「TFE」）與全氟-3,6-二氧-4-甲基-7-辛烯磺酸（「PSEPVE」）之共聚合物氘化，並以下列方式製成為一在d2o中之膠體分散液。可將在磺酸中每987克（每一酸性位點該共聚物之重量）具有一質子的聚（TFE-PSEPVE)製成D20分散液，其使用之製程類似於美國專利第6,150,426號之實例1，第2部分的製程，除了其溫度為約270°C且以D20取代水。實例3 此實例說明一氘化之導電聚合物，該聚合物摻雜一氘化 HFAP。氘化之。比咯，（「D5-Py」）（化學式量：72.12)係購自 Aldrich Chemical Company (Milwaukee，WI)。此褐色液體在使用前係於減壓下分餾。其無色餾出物係藉由13C NMR 光譜法加以特徵化以確定其結構。以下列方式在D-聚（TFE-PSEPVE)/D2分散液中進行D5-Py之聚合。先將製備於實例1之70.2 g的D-聚（TFE- 145486.doc -54· 201127895 PSEPVE)/D20於500 mL樹脂鍋中秤重後再加入14 g D20。該D-聚（TFE-PSEPVE)/D20之量代表8.14mmol的酸。將該鍋以一玻璃蓋加蓋，該蓋具有一上方攪拌器。一邊攪拌該 D-聚（TFE-PSEPVE)/D20，一邊將 0.135 g (0.26 mmol)硫酸鐵以及0.62 g (2.6 mmol)預先溶解於10 mL之Na2S2〇8加入該D-聚（TFE-PSEPVE)/D20中。稍後，將預先溶解於7 mL 〇2〇之0.175呂（2.43 111111〇1)的〇5-?}^在一分鐘内加入至該混合物中。在D5-Py加入後立即開始聚合反應。使該聚合反應進行10分鐘。成分之加入與聚合作用皆在氮氛圍中進行。1 0分鐘結束後，於樹脂鋼中加入Dowex M-43樹脂並混合約5分鐘。在以417渡紙進行真空過渡後，將Dowex M-3 1 Na+樹脂加入至該混合物中並混合約5分鐘。將所得材料再次以417濾紙進行真空過濾。將該摻雜D-聚（TFE-PSEPVE)之說化聚吼p各的D20分散液（「聚（D5-Py)/D-聚 (TFE-PSEPVE)」再次以離子交換樹脂加以處理，以進一步純化該分散液，在該分散液中僅含有1.79 ppm的硫酸鹽與0.79 ppm的氣化物。該分散液之固體％經測定為4.3%並且pH經測定為5.2。其鑄造膜在一乾箱中於275°C下烘烤30 分鐘，並且其導電度在室溫下經測定為〜1 X 1 (T6 S/cm。實例4 此實例顯示一裝置之製造與性能，該裝置係使用聚（D5-Py)/D-聚（TFE-PSEPVE)作為其電洞注入層。該裝置在一玻璃基板上具有下列結構：陽極=銦錫氧化物（ITO) : 50 nm 145486.doc •55- 201127895 電洞注入層=聚（〇5-Py)/D-聚（TFE-PSEPVE) (45 nm) 電洞傳輸層=一非經交聯之芳胺聚合物（2〇 nm) 電活性層=13 :1主體：摻雜劑（4〇 nm)。該主體為一 88〇/〇經氣化之二^•基蒽衍生物。該摻雜劑為一電致發光雙（二芳基胺基）疾（bis(diarylamino)chrysene)衍生物。電子傳輸層=一金屬喹啉衍生物（1 0 nm) 陰極=CsF/Al (1.0/100 nm) 藉由結合溶液加工及熱蒸链技術來製造〇LED裝置。使用來自Thin Film Device, Inc之圖案化氧化銦錫（IT〇)塗布玻璃基板。這些ΙΤΟ基板係基於塗布有ΙΤ〇之c〇rning 1737 玻璃，其具有30歐姆/平方的薄片電阻及8〇%的光穿透率。在水性清潔劑溶液中超音波清潔該些圖案化之IT〇基板，並以蒸餾水加以潤洗。隨後在丙酮中超音波清潔該圖案化之ΙΤΟ，以異丙醇加以潤洗，然後在氮氣流中乾燥。在該裝置即將製造前，以紫外光臭氧（uv 〇z〇ne)處理該些已清潔之圖案化的IT0基板1〇分鐘。在冷卻後，立即將來自實例3之聚（D5-Py)/D-聚（TFE-PSEPVE)的D20分散液旋轉塗布於該ITO表面並加熱以移除溶劑。在冷卻後，接著以一電洞傳輸材料之溶液旋轉塗布該些基板，然後再加熱以移除溶劑。在冷卻後，以該發射層溶液旋轉塗布該些基板，然後再加熱以移除溶劑。遮罩該些基板，並將其放入一真空室中。使用熱蒸鍍來沉積電子傳輸層，接著沉積一 CSF層。接著在真空中更換遮罩，並藉由熱蒸鍍沉積一 A1 層。使該真空室排氣，並使用一玻璃蓋、乾燥劑 145486.doc -56- 201127895 (dessicant)及Uv可固化環氧化物封裝該些裝置。藉由量測下列數據來特徵化OLED樣本，包括（1)電流-電壓（I-V)曲線’（2)電致發光輻射率對電壓之變化，及（3)電致發光光譜對電壓之變化。所有三個量測同時執行，並由一電腦控制。藉由將該LED之電致發光輻射率（radiance)除以運行該裝置所需之電流，而決定該裝置在某一電壓處的電流效率。其單位為Cd/A。將該電流效率乘以pi(7t)，再除以操作電壓，得出功率效率。其單位為lm/w。以相同方式製成四個裝置。該裝置結果係給出於表1。表1.裝置效能實例 CIE <Xy) 電壓 (V) C.E. (cd/A) E.Q.E. (%) P.E. (lm/W) 哥命測試電流密度 (mA/cm2) 壽命測試發光強度 (nits) 原始T50 ㈨預測壽命期 T50 @1000 4-1 0.138, 0.116 4.5 4.9 5.0 3.5 134 5851 636 llltO 12816 4-2 0.138, 0.116 4.6 5.0 5.0 3.4 123 5267 701 11813 4-3 0.137, 0.119 4.4 5.5 5.5 3.9 132 6120 600 13051 4-4 0.136, 0.120 4.4 5.4 5.4 3.9 125 5996 795 16701 *所有資料@ 1000 nits，CE=電流效率；ciEx和CIEy為根據 C.I.E.色度圖（c〇mmissi〇n Internati〇nale 心 L Eclairage，193 1)的χ和y顏色座標。原始T5〇係一裝置達到初始發光強度一半時的時間（以小時計），該初始發光強度係於壽命測試發光強度時所給定。預測 Τ50係於1000 nits時的預測壽命期，其使用一加速因子 1.7。應留意的是，並非上文一般性描述或實例中所述之動作 145486.doc •57- 201127895 都是必要的，特定動作之一部分可能並非需要的，並且除了所描述之動作外，可進一步執行一或多個其他動作◊此外，所列動作之次序不必然是執行該等步驟之次序。在上述說明中，已描述關於特定實施例之概念。然而，該項技藝之一般技術人士中之一理解在不脫離下面申請專利範圍所述之本發明的範疇下可進行各種修訂和變更。因此，應將本說明書與圖式視為說明性而非限制性之觀念，且意欲將所有這類修改涵括於本發明之範_中。刖文已針對特定實施例之效益、其他優點及問題解決方案加以闡述。然而，不可將效益、優點、問題解決方案以々何可使這些效益、優點或問題解決方案更為突顯的特徵解讀為是任何或所有專利巾請範圍之關鍵、必需或必要特徵。應田理解為了清楚說明起見，本文所述之各實施例内容切某些特徵，亦可以組合之方式於單獨實施例中別加以提供。相反地，簡潔起見’本文所述許多特徵於同一實施例中，其亦可分別提供或提供於任何次組合中。本文所指定之各種範圍内的數值的使用係恰如所述之範圍内的最小值及最大值的近似值，其使用「約為」作表不。以此方式，上文及下文所述之範圍可作些微變動只 s ^值在°亥等氣圍内’該等些微變動的數值實質上達到相 =果。並且，這些範圍之揭露意欲成為一連續範圍，其 :括最小與最大平均值間的各個數值，各個數值包括當一一八有某值之成分與其他不同值之成分混合時所產生的分 145486.doc -58- 201127895 數值。再者，當揭露較寬與較窄的範圍時，本發明之規劃包含使某一範圍之最小值配合另一範圍之最大值，且反之亦然。【圖式簡單說明】本發明係以範例的方式說明並且隨附的圖式並不造成限制。圖1A包括一有機場效電晶體（OTFT)的示意圖，其顯示此裝置在底部接觸模式（bottom contact mode)下的活性層相對位置。圖1B包括一有機場效電晶體（〇 τρτ)的示意圖，其顯示此一裝置在頂部接觸模式（top c〇ntact m〇de)下的活性層相對位置。圖ic包括一有機場效電晶體（0TFT)的示意圖，其顯示此裝置在底部接觸模式下的活性層相對位置並且頂部具有閘極。圖1D包括一有機場效電晶體（〇TFT)的示意圖，其顯示此一裝置在底部接觸模式下頂部具有閘極的活性層相對位置並且頂部具有閘極。圖2包括一有機電子裝置之另—實例的示意圖。圖3包括一有機電子裝置之另一實例的示意圖。熟習該技術者將瞭解，圖式中之物件係為達成簡單及清楚之目的而說明，不一定按比例繪製。例如，在該等圖式中，某#物件的尺寸相對於其他物件可能有所放大，以有助於對實施例的暸解。 145486.doc -59· 201127895 【主要元件符號說明】 102 閘極 104 絕緣層 106 源極 108 汲極 110 有機半導體層 112 基板 200 裝置 210 陽極層 220 電洞注入層 230 電洞傳輸層 240 電活性層 241 次像素單元 242 次像素單元 243 次像素單元 250 電子傳輸層 260 陰極層 145486.doc - 60 -Cs2C〇3 to lower the operating voltage. This layer can be referred to as an electronic injection layer. Only the cathode layer 26G is formed by a chemical or physical vapor deposition process. In some embodiments, the cathode layer is patterned, please refer to the polar layer 21 上述 described above. In some embodiments, 'in order to prevent unwanted, an encapsulation layer is deposited on the contact layer 260 (there are no components such as water and oxygen entering the device 2). These components can cause encapsulation of the organic layer 240. The layer is a barrier layer or film. A glass cover. A detrimental effect. In an embodiment, in an embodiment, the encapsulation layer is a glass, although not shown, it should be understood that the device 2 can include an additional layer. Other layers known or unknown in the art may be used. Further, any of the above layers may include two or more sub-layers, or may form a layer-like structure. Part or all of the anode layer 21 , the hole injection layer 22 , the hole transport layer 230 , the electron transport layer 25 , the cathode layer 26 , and other layers are processed, in particular, surface treated to increase the The electrical street carrier transport efficiency or other physical properties of the device. For each component layer, the selected material is preferably determined by considering the operational life, manufacturing time and complexity factors of the device, and familiarity. The technique Other considerations known to others balance the goal of providing a device with high device performance. It should be understood that for those of ordinary skill in the art, determining the optimal composition, composition, and composition identification It is a conventional technique. In one embodiment, the different layers have the following thickness ranges: anode 145486.doc • 51 · 201127895 210, 500-5000 A, in one embodiment 1000-2000 A; hole injection Layer 220 '50-3 000 A, in one embodiment 200_1000 A; selective hole transport layer 230, 5〇-2〇00 A, in one embodiment 200-1000 A; electroactive layer 240, 10-2000 A, in one embodiment 200-1000 A; selective electron transport layer 250, 50-2000 A, in one embodiment 200-1000 A; cathode 260, 200-10000 A, In one embodiment 300-5000 A. The relative thickness of each layer can affect the position of the electron-hole recombination zone in the device and thus affect the emission spectrum of the device. Therefore, the thickness of the electron transport layer should be selected. So that the electron hole recombination zone is located in the luminescent layer. The ratio will depend on the 4-cut nature of the material used. In operation, a voltage from an appropriate power supply (not shown) will be applied to the device 200. The current thus traverses through the device 2 Electrons enter the organic polymer layer to release protons. In some 〇led, so-called active matrix OLED displays, individual depositions of electroactive organic films can be excited by the t-stream, resulting in individual pixel light. Emission. In a 4_OLED, the so-called passive matrix rib display, the electroactive organic film/stacking can be excited by the rows and columns of electrical contact layers. Methods and materials similar or equivalent to those described herein can be used in the practice of testing the invention, but suitable methods and materials are described below. All publications, patent claims, patents, and other references herein are hereby incorporated by reference in their entirety. In the event of a conflict, the present specification, including package = meaning, shall prevail. In addition, the material materials and method examples are only illustrative, and ^^ 立立, 月Γ生 negative and not intended to be restricted. 145486.doc •52- 201127895 EXAMPLES Example 1 This example illustrates the deuteration of a HFAP to form a deuterated HFAP. It further illustrates the preparation of a deuterated HFAP dispersion in cerium oxide (〇2〇). A copolymer of tetrafluoroethylene ("TFE") and perfluoro-3,6-dioxo-4-indolyl-7-octenesulfonic acid ("PSEPVE") is vaporized and made into one in the following manner. The colloidal dispersion in 〇2〇. First, a poly(TFE psEpvE) having a proton in a sulfonic acid per 987 g (weight of the copolymer per acid site) is made into an aqueous dispersion. The process of use is similar to that of U.S. Patent No. 6,15. Example 1, Example 426, Part 2, except that the temperature is about 27 〇 <) (: The non-deuterated poly(TFE-PSEPVE) dispersion is converted to poly(TFE-PSEPVE) on a tray. a free-flowing solid sheet having a liquid depth of no greater than 5/8". The tray is then cooled to below (TC to freeze the aqueous dispersion. Once frozen, it is passed through a no more than 1 mm Hg Part of the true second / C force until most of the moisture is removed. The partially dried solid is then heated to about 3 〇c under turbulent pressure to completely remove moisture without coalescing the polymer. A non-deuterated poly(TFE-pSEPVE) solid flake (pre-dried in vacuum drying to remove moisture) is placed in a metal cylindrical tube pre-purged with nitrogen. It will be purchased from Cambridge lS0t0pe Lab, ―15之g 〇2〇 Immediately add to the tube containing the poly (TFE-PSEPVE). Cap the tube, Heated to a temperature of about 27 〇t in a pressure laboratory for a short period of time and then cooled to the chamber to ensure that the 6 HAI solid flakes were converted into poly (TFE-PSEPVE) in D2 〇. In addition, in extreme excess The protons in the poly (TFE_ 145486.doc •53.201127895 PSEPVE) have been exchanged with hydrazine, and the poly (TFE-PSEPVE) is finished. The sinking in D20 (TFE- PSEPVE) ("D-poly(TFE-PSEPVE)") dispersion is further processed to remove larger particles. The weight % of the D-poly (TFE-PSEPVE) in the D20 dispersion is determined by the method of weight measurement 11.34 wt.%, based on the total weight of the dispersion. Example 2 This example illustrates the direct method of forming a deuterated HFAP with a deuterated HFAP dispersion in cerium oxide (D20). The copolymer of ethylene ("TFE") and perfluoro-3,6-dioxo-4-methyl-7-octenesulfonic acid ("PSEPVE") is deuterated and made into a d2o in the following manner. Colloidal dispersion. Poly (TFE-PSEPVE) having a proton per 987 g (weight of the copolymer per acid site) can be made into D20 The dispersion is used in a process similar to that of Example 1, U.S. Patent No. 6,150,426, part 2, except that its temperature is about 270 ° C and water is replaced by D 20. Example 3 This example illustrates a conductive polymer The polymer was doped with a deuterated HFAP. Deuterated. ("D5-Py") (chemical formula: 72.12) was purchased from Aldrich Chemical Company (Milwaukee, WI). This brown liquid was fractionated under reduced pressure before use. Its colorless distillate was characterized by 13C NMR spectroscopy to determine its structure. The polymerization of D5-Py was carried out in a D-poly(TFE-PSEPVE)/D2 dispersion in the following manner. 70.2 g of D-poly (TFE-145486.doc -54·201127895 PSEPVE)/D20 prepared in Example 1 was weighed in a 500 mL resin kettle and then 14 g of D20 was added. The amount of D-poly(TFE-PSEPVE)/D20 represents 8.14 mmol of acid. The pan was capped with a glass lid with an upper agitator. While stirring the D-poly(TFE-PSEPVE)/D20, 0.135 g (0.26 mmol) of iron sulfate and 0.62 g (2.6 mmol) were previously dissolved in 10 mL of Na2S2〇8 to the D-poly (TFE-PSEPVE). /D20. Later, 0.175 liter (2.43 111111 〇 1) of 〇5-?}, previously dissolved in 7 mL of 〇2〇, was added to the mixture in one minute. The polymerization was started immediately after the addition of D5-Py. The polymerization reaction was allowed to proceed for 10 minutes. The addition and polymerization of the ingredients are carried out in a nitrogen atmosphere. After the end of 10 minutes, Dowex M-43 resin was added to the resin steel and mixed for about 5 minutes. After a vacuum transition with 417 paper, Dowex M-3 1 Na+ resin was added to the mixture and mixed for about 5 minutes. The resulting material was again vacuum filtered on 417 filter paper. The D20 dispersion ("poly(D5-Py)/D-poly(TFE-PSEPVE)" of each of the D-poly(TFE-PSEPVE) doped poly(p) is again treated with an ion exchange resin to The dispersion was further purified, containing only 1.79 ppm of sulfate and 0.79 ppm of vapor in the dispersion. The % solids of the dispersion was determined to be 4.3% and the pH was determined to be 5.2. The cast film was in a dry box. Bake at 275 ° C for 30 minutes, and its conductivity was determined to be ~1 X 1 at room temperature (T6 S/cm. Example 4 This example shows the manufacture and performance of a device using poly(D5) -Py)/D-poly (TFE-PSEPVE) as its hole injection layer. The device has the following structure on a glass substrate: Anode = Indium Tin Oxide (ITO): 50 nm 145486.doc • 55- 201127895 Electricity Hole injection layer = poly(〇5-Py)/D-poly(TFE-PSEPVE) (45 nm) hole transport layer = a non-crosslinked aromatic amine polymer (2 〇 nm) electroactive layer = 13: 1 host: dopant (4 〇 nm). The host is a 88 〇 / 〇 gasified bismuth derivative. The dopant is an electroluminescent bis(diarylamine) disease (bis(diarylamino) ) chrysene) derivative. electron transport layer = one metal quinoline derivative (10 nm) cathode = CsF / Al (1.0 / 100 nm) 〇 LED device is fabricated by combining solution processing and thermal evaporation chain technology. Patterned indium tin oxide (IT〇) coated glass substrates of Thin Film Device, Inc. These germanium substrates are based on c〇rning 1737 glass coated with tantalum, having a sheet resistance of 30 ohms/square and 8% light Permeability. The patterned IT(R) substrate is ultrasonically cleaned in an aqueous detergent solution and rinsed with distilled water. The patterned crucible is then ultrasonicated in acetone, rinsed with isopropanol, and then Drying in a stream of nitrogen. The cleaned patterned IT0 substrate was treated with ultraviolet light ozone (uv 〇z〇ne) for 1 minute before the device was manufactured. Immediately after cooling, the polymer from Example 3 was D5-Py)/D-poly(TFE-PSEPVE) D20 dispersion is spin-coated on the surface of the ITO and heated to remove the solvent. After cooling, the substrate is then spin coated with a solution of a hole transport material, and then Reheat to remove the solvent. Thereafter, the substrates are spin-coated with the emissive layer solution, and then heated to remove the solvent. The substrates are masked and placed in a vacuum chamber. The electron transport layer is deposited using thermal evaporation, followed by deposition. A CSF layer. The mask is then replaced in a vacuum and an A1 layer is deposited by thermal evaporation. The vacuum chamber was vented and the devices were packaged using a glass lid, desiccant 145486.doc -56-201127895 (dessicant) and Uv curable epoxy. The OLED samples were characterized by measuring the following data, including (1) current-voltage (I-V) curve '(2) electroluminescence radiance versus voltage change, and (3) electroluminescence spectrum versus voltage change. All three measurements are performed simultaneously and controlled by a computer. The current efficiency of the device at a certain voltage is determined by dividing the radiance of the LED by the current required to operate the device. Its unit is Cd/A. This current efficiency is multiplied by pi (7t) and divided by the operating voltage to obtain power efficiency. Its unit is lm/w. Four devices were fabricated in the same manner. The device results are given in Table 1. Table 1. Example of device performance CIE <Xy) Voltage (V) CE (cd/A) EQE (%) PE (lm/W) Life test current density (mA/cm2) Life test luminous intensity (nits) Original T50 (9) Life expectancy T50 @1000 4-1 0.138, 0.116 4.5 4.9 5.0 3.5 134 5851 636 llltO 12816 4-2 0.138, 0.116 4.6 5.0 5.0 3.4 123 5267 701 11813 4-3 0.137, 0.119 4.4 5.5 5.5 3.9 132 6120 600 13051 4-4 0.136, 0.120 4.4 5.4 5.4 3.9 125 5996 795 16701 *All information @ 1000 nits,CE=current efficiency; ciEx and CIEy are based on CIE chromaticity diagram (c〇mmissi〇n Internati〇nale heart L Eclairage,193 1 ) χ and y color coordinates. The original T5 is the time (in hours) at which the initial luminous intensity reaches half of the initial luminous intensity, which is given at the lifetime test luminous intensity. The predicted Τ50 is the predicted lifetime at 1000 nits, which uses an acceleration factor of 1.7. It should be noted that actions 145486.doc • 57- 201127895, which are not described in the general description or examples above, are necessary, and some of the specific actions may not be required and may be further performed in addition to the actions described. One or more other acts ◊ In addition, the order of the actions listed is not necessarily the order in which the steps are performed. In the above description, the concept of a particular embodiment has been described. However, one of ordinary skill in the art understands that various modifications and changes can be made without departing from the scope of the invention as described in the following claims. Therefore, the specification and drawings are to be regarded as illustrative and not restrictive The description of the benefits, other advantages and problem solutions of specific embodiments has been presented. However, the benefits, advantages, and solutions to problems that make these benefits, benefits, or problem resolutions more prominent are not interpreted as critical, necessary, or necessary features of any or all of the patent claims. The present invention is described in terms of certain features and may be combined in a separate embodiment. Conversely, for the sake of brevity, many of the features described herein are in the same embodiment, which may also be provided separately or in any sub-combination. The use of numerical values in the various ranges specified herein is intended to be an approximation of the minimum and maximum values within the stated range, which is "about" In this way, the ranges described above and below may be slightly varied only if the value of s ^ is within the range of ° Hz, etc. The values of these slight variations substantially reach the phase = fruit. Moreover, the disclosure of these ranges is intended to be a continuous range, which includes the various values between the minimum and maximum average values, and the various values include the points that are produced when the components of the one-eighth value are mixed with the components of the other different values. .doc -58- 201127895 Value. Moreover, when exposing a wider and narrower range, the present invention includes planning to match the minimum of a range to the maximum of another range, and vice versa. BRIEF DESCRIPTION OF THE DRAWINGS The present invention is illustrated by way of example and not limitation. Figure 1A includes a schematic diagram of an organic field effect transistor (OTFT) showing the relative position of the active layer of the device in a bottom contact mode. Figure 1B includes a schematic diagram of an airport effect transistor (〇τρτ) showing the relative position of the active layer of the device in top contact mode (top c〇ntact m〇de). Figure ic includes a schematic diagram of an organic field effect transistor (0TFT) showing the relative position of the active layer in the bottom contact mode and the gate at the top. Figure 1D includes a schematic diagram of an organic field effect transistor (〇TFT) showing that the device has an active layer relative position with a gate at the top and a gate at the top in the bottom contact mode. Figure 2 includes a schematic view of another example of an organic electronic device. Figure 3 includes a schematic diagram of another example of an organic electronic device. Those skilled in the art will understand that the objects in the drawings are illustrated for simplicity and clarity and are not necessarily to scale. For example, in these figures, the size of an #object may be magnified relative to other objects to facilitate an understanding of the embodiments. 145486.doc -59· 201127895 [Description of main component symbols] 102 gate 104 insulating layer 106 source 108 drain 110 organic semiconductor layer 112 substrate 200 device 210 anode layer 220 hole injection layer 230 hole transport layer 240 electroactive layer 241 sub-pixel unit 242 sub-pixel unit 243 sub-pixel unit 250 electron transport layer 260 cathode layer 145486.doc - 60 -

Claims

201127895 七、申請專利範圍：201127895 VII. Patent application scope:

一組成物，其包含（1)或者（2)·· 一高度氟化之酸 (1)-沉化之導電聚合物，該聚合物摻雜聚合物，或 y (2)(a)—氘化之導電聚合物合性酸；以及該聚合物摻雜一非氟化之聚 (b)至少一尚度氟化之酸聚合物。 2. 如申請專利範圍第1項所述之組成物，其中該導電聚合物係選自由-氣化聚嚷吩、一說化聚笨胺、一識。比 :、一氖化聚合性稍合多環雜芳族、-氣化聚(胺㈣ 1·) _L述物賀之共聚合物以及上述物質之組合所組成之群組。士申-月專利範圍第2項所述之組成物，其中該導電聚合物係選自由聚（d6_3,4_伸乙二氧嗟吩）、聚（d5♦各）、聚 (D?苯胺）、聚（全氘_4胺基吲哚）、聚（全氘胺基吲哚）、聚（全氣塞吩并（2,3-b)嗟吩）、聚（全氣·嘆吩并（3,2_ b)塞力）與聚（全氘_噻吩并（3,4_b)噻吩）所組成之群組。 4. 如申請專利範圍第1項所述之組成物，其中該高度氟化之酸聚合物係至少95%經氟化。 5. 如申請專利範圍第1項所述之組成物，其中該高度氤化之酸聚合物係選自一磺酸與一磺醯亞胺。 6. 如申請專利範圍第1項所述之組成物，其中該高度氟化之酸聚合物為一具有全氟-醚-磺酸側鏈之全氟烯烴。 7. 如申請專利範圍第1項所述之組成物，其中該高度氟化 145486.doc 201127895 之酉文I σ物為全I化並且為一氛化酸。 8.如申請專利範圍第1項所述之組成物，其中該氘化之導電聚合物係摻雜該高度氟化之酸聚合物。 9·如U利乾圍第8項所述之組成物，其中該組成物係選自由摻雜全氟化之氘化酸聚合物的聚（D^EDOT)、摻雜一全氟化之氘化酸聚合物的聚（D5-Py)以及摻雜一全氟化之氘化‘聚合物的〇7_?抓〗所組成之群組。 1〇.如申請專利範圍第i項所述之組成物，其中該氛化之導電聚合物係摻雜一非氟化之聚合性酸。申咕專利範圍第i 〇項所述之組成物，其中該氘化之導電聚合物係選自由捧雜〜聚苯乙稀續酸的D6-聚（3,4_伸乙二氧噻吩）、摻雜A—聚苯乙烯磺酸的〇4_聚吡咯與摻雜 Du-聚（2-丙稀醯胺_2甲基+丙績酸）的D7_聚苯胺所之群組。 12. 種組成物，其包含一氛化之液體介質，於其中分散有 ⑷—氘化之導電聚合物’該聚合物摻雜-非氟化之聚合性酸以及（b)—高度氟化之酸聚合物。 13. 種組成物，其包含一氛化之液體介質，於其中分散有 -筑化之導電聚合物，該聚合物擦雜—高度氟化之酸聚合物。 14. -種有機電子裝置，其包含至少一層，該至少一層包含 -上述申請專利範圍之任何_者所述的氣化之導電聚合物。 15. 如申請專利範圍第14項所述之裝置，其包含： 145486.doc 201127895 一基板一絕緣層；一閘極；一源極；一汲極；以及其中至少一電極包含_ 缘声…聚物’並且其中該絕緣層°亥閘極、該半導體声、兮、、s & ^ 床Μ別 θ 4，原極與該汲極可以任何川g 序排列，而條件為該閘極盥任何順 μ , . /、4 +導體層兩者皆接觸該絕緣層〇亥源極與該汲極兩者皆桩龅 > , 緣極彼此未互相接觸。牛導體層H亥些電 145486.doca composition comprising (1) or (2)·· a highly fluorinated acid (1)-deposited conductive polymer, the polymer doped polymer, or y (2)(a)-氘a conductive polymer-compatible acid; and the polymer is doped with a non-fluorinated poly(b) at least one fluorinated acid polymer. 2. The composition of claim 1, wherein the conductive polymer is selected from the group consisting of: gasified polybenzazole, polyphosphoric acid, and polymorph. Ratio: A group consisting of a polycondensed polycyclic heteroaromatic group, a gasified poly(amine (tetra) 1·), a conjugated copolymer, and a combination of the above. The composition of the second aspect of the invention, wherein the conductive polymer is selected from the group consisting of poly(d6_3,4_ethylenedioxy porphin), poly(d5♦), poly(D-aniline) , poly (all 氘 4 amino hydrazine), poly (full guanamine hydrazine), poly (full gas pheno (2,3-b) porphin), poly (all gas sighs) 3,2_ b) Settlement) and a group consisting of poly(all 氘-thieno(3,4_b)thiophene). 4. The composition of claim 1 wherein the highly fluorinated acid polymer is at least 95% fluorinated. 5. The composition of claim 1, wherein the highly deuterated acid polymer is selected from the group consisting of monosulfonic acid and monosulfonimide. 6. The composition of claim 1, wherein the highly fluorinated acid polymer is a perfluoroolefin having a perfluoro-ether-sulfonic acid side chain. 7. The composition of claim 1, wherein the highly fluorinated 145486.doc 201127895 is I-I and is an acidified acid. 8. The composition of claim 1, wherein the deuterated conductive polymer is doped with the highly fluorinated acid polymer. 9. The composition of claim 8, wherein the composition is selected from the group consisting of poly(D^EDOT) doped with a perfluorinated bismuth acid polymer, doped with a perfluorinated ruthenium. The poly(D5-Py) of the acid polymer and the group consisting of a perfluorinated deuterated polymer. The composition of claim i, wherein the condensed conductive polymer is doped with a non-fluorinated polymeric acid. The composition of claim i, wherein the deuterated conductive polymer is selected from the group consisting of D6-poly(3,4-ethylenedioxythiophene), which is a heteropoly-polystyrene acid. A group of D7-polyphenylene doped with A-polystyrenesulfonic acid and D7-polyaniline doped with Du-poly(2-acrylamido-2-methyl+propionic acid). 12. A composition comprising an aqueous liquid medium in which (4)-deuterated conductive polymer 'the polymer doped-non-fluorinated polymeric acid and (b) - highly fluorinated Acid polymer. 13. A composition comprising an aqueous liquid medium in which a conductive polymer is dispersed, the polymer is rubbed - a highly fluorinated acid polymer. 14. An organic electronic device comprising at least one layer comprising: the vaporized electrically conductive polymer of any of the above-identified patents. 15. The device of claim 14, comprising: 145486.doc 201127895 a substrate-insulation layer; a gate; a source; a drain; and wherein at least one of the electrodes comprises a _ edge sound... And the insulating layer is at the gate, the semiconductor sound, 兮, s & ^ bed discrimination θ 4, the original pole and the drain can be arranged in any order, and the condition is that the gate is any Both the S, . , and 4 + conductor layers are in contact with the insulating layer, and both the source and the drain are stacked. The edges are not in contact with each other. Cattle conductor layer H Hai some electricity 145486.doc